TW202012421A - 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; Q1 is a specific group of (a+b) valence having at least (a+b) Si atoms independently of each other; Q2 is a divalent hydrocarbon group of 1 to 20 carbon atoms independently; and X is a group represented by a, b, c wherein R2 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 hardening composition

The present invention relates to an active energy ray curable composition. Specifically, it relates to an active energy ray-curable composition containing a photo-cation-curable resin, and particularly to an activity that is also applicable as a photo-cation hard coating agent and useful as an ultraviolet-curable antifouling surface-imparting agent Energy ray hardening composition.

The hard coating agent (or a coating having a role as a hard coating layer) is hardened by coating on the surface of various articles represented by plastic resin, and as a material that can protect the surface of the article and impart new functions to the surface of the article is very wide Used in a range of applications.

In addition to the hardness, abrasion resistance, chemical resistance, and durability required in the past, such hard coating agents also require water and oil repellency, antifouling properties, fingerprint resistance, Weather resistance, friction, antistatic agent, anti-fogging, hard-to-focus and anti-reflective features are further enhanced. Especially in recent years, the improvement of dirt prevention and dirt wiping properties is required.

The active energy ray hardening type hard coating agents include ultraviolet and electron beam hardening type hard coating agents and thermosetting type coating agents. Examples of the ultraviolet/electron beam hardening type hard coating agent include, for example, a hard coating agent containing an acrylic group hardened by radical polymerization by ultraviolet rays. In recent years, it has been discussed that by adding a very small amount of ultraviolet hardening type hard coating agent, in addition to the characteristics of the coating agent before addition, it can impart water and oil repellency and antifouling properties and fingerprint resistance to the resulting hardened surface. Fluorine-containing compounds.

The inventors have proposed in Patent Documents 1 to 4 that the additives used as hard coating agents for ultraviolet or electron beam hardening can be used better, and the resulting hardened product can be provided with water and oil repellency, antifouling properties, and fingerprint resistance. Fluorine-containing compounds. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2010-053114 [Patent Document 2] Japanese Patent Application Publication No. 2010-138112 [Patent Document 3] Japanese Patent Application Publication No. 2010-285501 [Patent Document 4] Japanese Patent Laid-Open No. 2011-241190

[Problem to be solved by invention]

As used for the above purpose, the ultraviolet (UV) hardening type acrylic hard coating agent hardened by free radical polymerization has fast curing, and can be used as an ingredient. The acrylic compound or initiator is rich in variety and easy to adjust the composition in accordance with the purpose advantage. On the other hand, there is a fundamental problem that is caused by the radical polymerization of the acrylic group, which is caused by the fact that the curing shrinkage under the influence of the hardening inhibition due to oxygen is large.

In particular, the hardening due to oxygen is hindered in the air interface of the coating film obtained by the hard coating composition, and the closer it is to the outermost surface side, the more susceptible it is, which becomes a major obstacle when imparting antifouling properties to the outermost surface. Moreover, the hardening shrinkage due to the polymerization of acrylic acid tends to increase the influence of curling and cracking accompanying hardening shrinkage during multifunctionalization in order to increase the hardness. It is required to increase the hardness of hard coating agents in recent years. With further improvement, it becomes difficult to cope with acrylic polymerization type.

On the other hand, UV-curable cationic polymerization-based hard coating agents having compounds such as epoxy groups, oxetanyl groups, and vinyl ether groups have excellent surface hardening properties due to the lack of polymerization resistance due to oxygen. Moreover, even when hardened, the volume shrinkage is smaller than that of the acrylic type (free radical polymerization type).

Therefore, in recent years, the development of UV cationic hardening type hard coating agents has been carried out in large quantities, and the requirements for imparting antifouling properties to cationic hard coating agents have also increased.

The present invention has been completed in view of the above circumstances, and its object is to provide a cured product that can impart a surface with excellent water and oil repellency, antifouling properties, and fingerprint resistance. Type antifouling surface-imparting agent useful active energy ray hardening composition. [Means to solve the problem]

(Rf、Q1、Q2、X、a、a’、b及a+b如下述)。As a result of active research by the present inventors to solve the above-mentioned problems, it has been found that the active energy ray includes a specific fluorine-containing epoxy-modified organosilicon compound (A) represented by the following general formula (1) and a photopolymerization initiator (B) The cured product of the curable composition (photo-cationic polymerizable composition) has excellent water and oil repellency, antifouling properties and fingerprint resistance on the surface, thus completing the present invention.

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

(式(1)中，Rf相互獨立為具有氟聚醚構造之數平均分子量400~40,000之一價或二價之基，Rf為一價基時，係以下述式表示：

(上述式中，j為1~3之整數，k為0~200之整數，k’為1~200之整數，l、m分別為1~100之整數)， Rf為二價基時，係以下述式表示：

(式中，r為2~6之整數，k、t分別為0~200之整數，但k+t為2~200，s為0~6之整數)，

(式中，j獨立為1~3之整數，h、i分別為0~200之整數，但h+i為2~300，各重複單位可以無規鍵結)，

(式中，r為2~6之整數，k、t分別為0~200之整數，但k+t為2~200，s為0~6之整數)，或

(式中，r為2~6之整數，k、t分別為0~200之整數，但k+t為2~200，s為0~6之整數)， Rf為一價基時，a’為1，a為1~6之整數，Rf為二價基時，a’為2，a為1，b為1~20之整數，a+b為3~21之整數， Q¹ 相互獨立為至少具有(a+b)個Si原子之(a+b)價之基，且以下述式表示：

(式中，a及b如前述，虛線表示鍵結鍵，具有a個重複之括弧內所示之單位的各矽原子與前述式(1)中之Rf鍵結，具有b個重複之括弧內所示之單位的各矽原子與前述式(1)中之Q² 鍵結，括弧內所示之單位的排列可為無規)， Q² 相互獨立為可包含醚鍵或酯鍵，且可具有環狀構造之碳數1~20之二價烴基， X相互獨立為下述式(I)或(II)表示之基，

(式(I)中，R¹ 相互獨立為氫原子或碳數1~20之非取代或取代之一價烴基，可包含醚鍵或酯鍵，可具有環狀構造)，

(式(II)中，R² 相互獨立為氫原子或碳數1~20之非取代或取代之一價烴基))， 該活性能量線硬化性組成物係賦予表面之水接觸角為100°以上的硬化物者。 [2] 如[1]之活性能量線硬化性組成物，其中前述式(1)中，以-Q² -X-表示之構造係自下述式(2)~(5)所示之基中選出者，

(上述式中，f為1~10之整數，e為0~5之整數，g為0~10之整數，f+2g+e於1~20之範圍內，n為1~20之整數，R² 相互獨立為氫原子或碳數1~20之非取代或取代之一價烴基)。 [3] 如[1]或[2]之活性能量線硬化性組成物，其中前述式(1)中，Q² 相互獨立為自下述式所示之基中選出者，

[4] 如[2]或[3]之活性能量線硬化性組成物，其中前述式(1)中，以-Q² -X表示之構造係下述式，

[5] 如[1]至[4]中任一項之活性能量線硬化性組成物，其中光聚合起始劑(B)為光酸產生劑。 [6] 如[1]至[5]中任一項之活性能量線硬化性組成物，其中光聚合起始劑(B)為重氮鎓鹽、錪鎓鹽、鋶鹽之任一者。 [7] 如[1]至[6]中任一項之活性能量線硬化性組成物，其中具有陽離子硬化性之化合物僅為(A)成分時，相對於(A)成分100質量份，(B)成分含有0.01~20質量份。 [8] 如[1]至[6]中任一項之活性能量線硬化性組成物，其中進而含有由(A)成分以外之1種以上之具有陽離子硬化性之化合物所成之(C)成分，相對於(A)成分與(C)成分之合計100質量份，(B)成分含有0.01~20質量份。 [9] 如[8]之活性能量線硬化性組成物，其中(C)成分係1分子中具有1個以上之環氧基、乙烯醚基、氧雜環丁基、羰基之任一者之化合物、脂肪族不飽和烴化合物、苯乙烯衍生物、雙環原酯、螺原碳酸酯、螺原酯或陽離子聚合性含氮化合物。 [10] 如[8]或[9]之活性能量線硬化性組成物，其中相對於(C)成分100質量份，(A)成分含有0.01~10質量份，硬化後之硬化物表面的水接觸角為100°以上。 [發明效果]That is, the present invention provides the following active energy ray curable composition. [1] An active energy ray hardening composition comprising an active energy ray hardening comprising a fluorine-containing epoxy-modified organosilicon compound (A) represented by the following general formula (1) and a photopolymerization initiator (B) Sexual composition,

(In formula (1), Rf is independently a monovalent or divalent group with a number average molecular weight of 400 to 40,000 having a fluoropolyether structure. When Rf is a monovalent group, it is represented by the following formula:

(In the above formula, j is an integer from 1 to 3, k is an integer from 0 to 200, k'is an integer from 1 to 200, l and m are integers from 1 to 100 respectively), when Rf is a divalent base, it is Expressed in the following formula:

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, but k+t is from 2 to 200, and s is an integer from 0 to 6),

(In the formula, j is independently an integer of 1~3, h and i are integers of 0~200, but h+i is 2~300, and each repeating unit can be randomly bonded),

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, but k+t is from 2 to 200, and s is an integer from 0 to 6), or

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, but k+t is from 2 to 200, and s is an integer from 0 to 6). When Rf is a monovalent base, a' Is 1, a is an integer from 1 to 6, when Rf is a divalent group, a'is 2, a is 1, b is an integer from 1 to 20, a+b is an integer from 3 to 21, and Q ^{1 is} independently A group having at least (a+b) valence of (a+b) Si atoms, and expressed by the following formula:

(In the formula, a and b are as described above, the dashed line represents a bonding bond, each silicon atom having a unit shown in a repeating parenthesis is bonded to Rf in the above formula (1), and having b repeating parentheses Each silicon atom of the unit shown is bonded to Q ² in the aforementioned formula (1), the arrangement of the units shown in parentheses may be random), Q ^{2 is} independent of each other and may include an ether bond or an ester bond, and may A divalent hydrocarbon group having a ring structure of 1 to 20 carbon atoms, X is independently a group represented by the following formula (I) or (II),

(In formula (I), R ^{1 is} independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and may include an ether bond or an ester bond, and may have a cyclic structure),

(In formula (II), R ^{2 is} independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms)), the active energy ray-curable composition imparts a water contact angle of 100° to the surface Those with hardened objects above. [2] The active energy ray-curable composition as described in [1], wherein the structure represented by -Q ² -X- in the aforementioned formula (1) is derived from the bases represented by the following formulas (2) to (5) Selected by

(In the above formula, f is an integer of 1-10, e is an integer of 0-5, g is an integer of 0-10, f+2g+e is in the range of 1-20, n is an integer of 1-20, R ^{2 is} independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms). [3] The active energy ray-curable composition according to [1] or [2], wherein in the aforementioned formula (1), Q ^{2 is} independently selected from the group represented by the following formula,

[4] The active energy ray-curable composition according to [2] or [3], wherein the structure represented by -Q ² -X in the aforementioned formula (1) is the following formula,

[5] The active energy ray-curable composition according to any one of [1] to [4], wherein the photopolymerization initiator (B) is a photoacid generator. [6] The active energy ray-curable composition according to any one of [1] to [5], wherein the photopolymerization initiator (B) is any one of a diazonium salt, a phosphonium salt, and a monium salt. [7] When the active energy ray-curable composition according to any one of [1] to [6], wherein the compound having cationic curability is only the component (A), relative to 100 parts by mass of the component (A), ( B) The component contains 0.01 to 20 parts by mass. [8] The active energy ray-curable composition according to any one of [1] to [6], which further contains (C) made of one or more cation-curable compounds other than the component (A) The component contains 0.01 to 20 parts by mass relative to 100 parts by mass of the total of the components (A) and (C). [9] The active energy ray-curable composition as described in [8], wherein the component (C) is one of having at least one epoxy group, vinyl ether group, oxetanyl group, or carbonyl group in one molecule Compounds, aliphatic unsaturated hydrocarbon compounds, styrene derivatives, bicyclic orthoesters, spiroorthocarbonates, spiroorthoesters or cationically polymerizable nitrogen-containing compounds. [10] The active energy ray-curable composition according to [8] or [9], wherein component (A) contains 0.01 to 10 parts by mass relative to 100 parts by mass of component (C), and water on the surface of the cured product after curing The contact angle is above 100°. [Effect of the invention]

The active energy ray-curable composition of the present invention can impart a hardened product with excellent water and oil repellency, antifouling properties and fingerprint resistance on the surface. Therefore, the active energy ray-curable composition can be suitably used as a photo-cationic coating agent and as an ultraviolet-curable antifouling surface-imparting agent that can be cured by photo-cationic polymerization.

The present invention will be described in detail below. The active energy ray-curable composition of the present invention is characterized by containing a fluorine-containing epoxy-modified organosilicon compound (A) and a photopolymerization initiator (B) shown below.

(式(1)中，Rf相互獨立為具有氟聚醚構造之數平均分子量400~40,000之一價或二價之基，Q¹ 相互獨立為至少具有(a+b)個Si原子之(a+b)價之後述特定基，Q² 相互獨立為可包含醚鍵或酯鍵且可具有環狀構造之碳數1~20之二價烴基，X為後述式(I)或(II)表示之基。且，Rf為一價基時，a’為1，a為1~6之整數。Rf為二價基時，a’為2，a為1，b為1~20之整數，a+b為3~21之整數)。The fluorine-containing epoxy-modified organosilicon compound (A) of the first component of the present invention is a cation-curable compound represented by the following general formula (1).

(In formula (1), Rf is independently a monovalent or divalent radical having a number average molecular weight of 400 to 40,000 with a fluoropolyether structure, and Q ^{1 is} independently a (a+b) Si atom (a +b) The specific group mentioned later, Q ^{2 is} independently a divalent hydrocarbon group of 1 to 20 carbon atoms which may include an ether bond or an ester bond and may have a cyclic structure, and X is represented by formula (I) or (II) described later And, when Rf is a monovalent group, a'is 1, a is an integer from 1 to 6. When Rf is a divalent group, a'is 2, a is 1, b is an integer from 1 to 20, a +b is an integer from 3 to 21).

In formula (1), X is independently a group represented by the following formula (I) or (II).

In formula (I), R ^{1 is} independently a hydrogen atom or a carbon number 1-20, preferably a carbon number 1-10, more preferably a carbon number 1-8 unsubstituted or substituted monovalent hydrocarbon group, which may include an ether bond or The ester bond may have a ring structure. Examples of the above-mentioned monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, hexyl, octyl, and decyl groups, vinyl groups, and allyl groups. Alkenyl such as alkyl, propenyl, butenyl, hexenyl, etc., cycloalkyl such as cyclopentyl, cyclohexyl, etc. In addition, a part or all of the hydrogen atoms of these hydrocarbon groups may be substituted with halogen atoms such as fluoromethyl, bromoethyl, trifluoropropyl, etc., substituted by halogen atoms such as chlorine, fluorine, and bromine. Preferably, R ¹ is a hydrogen atom.

In formula (II), R ^{2 is} independently a hydrogen atom or a carbon number 1-20, preferably a carbon number 1-10, more preferably a carbon number 1-8 unsubstituted or substituted monovalent hydrocarbon group. Examples of the above-mentioned monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, hexyl, octyl, and decyl groups, vinyl groups, and allyl groups. Alkenyl such as radical, propenyl, butenyl, hexenyl, etc. In addition, a part or all of the hydrogen atoms of these hydrocarbon groups may be substituted with halogen atoms such as fluoromethyl, bromoethyl, trifluoropropyl, etc., substituted by halogen atoms such as chlorine, fluorine, and bromine. Preferably, R ² is a hydrogen atom.

(式中，R² 如上述)。Examples of the structure represented by the above formula (I) or (II) are, for example, the following.

(In the formula, R ^{2 is} as described above).

In the above formula (1), Q ^{2 is} independently a C 1-20, preferably C 2-15 divalent hydrocarbon group, may have a cyclic structure, or may include an ether bond (-O-) or an ester in the middle Key (-COO-).

(上述式中，f為1~10之整數，e為0~5之整數，g為0~10之整數，f+2g+e為1~20之範圍內。較好f為1~6之整數，e為1或2，g為0~4之整數，f+2g+e為3~10之範圍內。n為1~20之整數，較好為2~15之整數)。In the above formula (1), Q ^{2 is} exemplified by, for example, the following.

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

An example of this Q ² is the following constructor.

In the above formula (1), as the structure represented by -Q ² -X, for example, the structures represented by the following formulas (2) to (5) are exemplified.

In the above formula, f, e, g, f+2g+e, n are as described above. As described above, R ^{2 is} preferably a hydrogen atom or a methyl group.

In the above formula (1), the structure represented by -Q ² -X is particularly preferably the following formula,

In the above formula (1), Q ^{1 is} independently a group having a (a+b) valence of at least (a+b) Si atoms. When Rf in the above formula (1) is a monovalent group, a'is 1, a is an integer of 1 to 6, preferably an integer of 1 to 4, and more preferably 1. When Rf is a divalent group, a'is 2, and a is 1. b is an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 2 to 4. Furthermore, a+b is an integer of 3-21, preferably a+b=an integer of 3-10, more preferably a+b=an integer of 3-6, and even better a+b=4 or 5.

Q ¹ has a (a+b) cyclic siloxane structure represented by the following formula.

In the above formula, a and b are as described above, and the dotted line indicates a bonding bond, each silicon atom having a unit shown in a repeating parenthesis is bonded to Rf in the above formula (1), having b repeating parentheses Each silicon atom in the unit shown is bonded to Q ² in the aforementioned formula (1). The arrangement of units shown in parentheses may be random.

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

(上述式中，j為1~3之整數，k為0~200之整數，較好為0~100之整數，k’為1~200之整數，較好為1~60之整數，l、m分別為1~100之整數)。The monovalent Rf is represented by the following formula.

(In the above formula, j is an integer from 1 to 3, k is an integer from 0 to 200, preferably an integer from 0 to 100, k'is an integer from 1 to 200, preferably an integer from 1 to 60, l, m is an integer from 1 to 100).

(上述式中，j為1~3之整數，k為0~200之整數，較好為0~100之整數，l、m分別為1~100之整數)。Among them, those represented by the following formula are preferred.

(In the above formula, j is an integer of 1 to 3, k is an integer of 0 to 200, preferably an integer of 0 to 100, and l and m are integers of 1 to 100, respectively).

(式中，r為2~6之整數，k、t分別為0~200之整數，但k+t為2~200，s為0~6之整數)。

(式中，j獨立為1~3之整數，h、i分別為0~200之整數，但h+i為2~300，各重複單位可以無規鍵結)。

(式中，r為2~6之整數，k、t分別為0~200之整數，但k+t為2~200，s為0~6之整數)。

(式中，r為2~6之整數，k、t分別為0~200之整數，但k+t為2~200，s為0~6之整數)。The divalent Rf is represented by the following formula.

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, but k+t is from 2 to 200, and s is an integer from 0 to 6).

(In the formula, j is independently an integer of 1~3, h and i are integers of 0~200, but h+i is 2~300, and each repeating unit can be randomly bonded).

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, but k+t is from 2 to 200, and s is an integer from 0 to 6).

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, but k+t is from 2 to 200, and s is an integer from 0 to 6).

(式中，j為1~3之整數，h、i分別為0~200之整數，但h+i為2~300，各重複單位可以無規鍵結)。Among them, it is particularly desired to be expressed by the following formula.

(In the formula, j is an integer of 1~3, h and i are integers of 0~200, but h+i is 2~300, and each repeating unit can be randomly bonded).

The compound (fluorinated epoxy-modified organosilicon compound) represented by the above general formula (1) can be produced by, for example, the following method. First, for the fluorine-containing compound (a) having an olefin group at the end, under the condition that SiH becomes excessive, the organosilicon compound (b) (silicon oxide) having 2 or more, preferably 3 or more SiH groups in the addition reaction molecule Alkanes or organosilicon compounds composed of two or more of them). Through this reaction, a fluorine-containing compound (c) having plural SiH groups is synthesized.

(上述式(6)中，於Rf⁰ 為一價時x為1，於Rf⁰ 為二價時x為2)。In particular, the compound (a) can be represented by the following formula (6).

(In the above formula (6), Rf ⁰ is a divalent to x is 1, x is at Rf ⁰ is a divalent 2).

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

(上述式中，j為1~3之整數，k為0~200之整數，較好為0~100之整數，k’為1~200之整數，較好為1~60之整數，l、m分別為1~100之整數)。In the above formula (7), Rf ² is represented by the following formula:

(In the above formula, j is an integer from 1 to 3, k is an integer from 0 to 200, preferably an integer from 0 to 100, k'is an integer from 1 to 200, preferably an integer from 1 to 60, l, m is an integer from 1 to 100).

(式中，r為2~6之整數，k、t分別為0~200之整數，但k+t為2~200，s為0~6之整數)。

(式中，j為1~3之整數，h、i分別為0~200之整數，但h+i為2~300)。In addition, in the above formula (8), Rf ¹ is represented by the following formula:

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, but k+t is from 2 to 200, and s is an integer from 0 to 6).

(In the formula, j is an integer of 1~3, h and i are integers of 0~200, but h+i is 2~300).

In addition, in the above formulas (7) and (8), Q ^{6 is} independently a bivalent organic group having a carbon number of 2 to 10, preferably a carbon number of 2, which may contain an oxygen atom, a nitrogen atom, or a silicon atom.

As an example of the above Q ^{6, the} following expression is used.

(式中，k為0~200之整數，較好為0~100之整數)。

(式中，j為1~3之整數，k’為1~200之整數，較好為1~60之整數)。

(上述式中，j為1~3之整數，l、m分別為1~100之整數)。

(式中，k為0~200之整數，較好為0~100之整數)。

(式中，k為0~200之整數，較好為0~100之整數)。Examples of the monovalent Rf ⁰ compound (a) include the following.

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100).

(In the formula, j is an integer of 1 to 3, and k'is an integer of 1 to 200, preferably an integer of 1 to 60).

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

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100).

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100).

(式中，r為2~6之整數，k、t分別為0~200之整數，較好為0~100之整數，但k+t為2~200，較好為3~150，s為0~6之整數)。

(式中，j獨立為1~3之整數，h、i分別為0~200之整數，較好為2~100之整數，但h+i為2~300，較好為4~200，各重複單位可以無規鍵結)。

(式中，r為2~6之整數，k、t分別為0~200之整數，較好為0~100之整數，但k+t為2~200，較好為3~150，s為0~6之整數)。

(式中，r為2~6之整數，k、t分別為0~200之整數，較好為0~100之整數，但k+t為2~200，較好為3~150，s為0~6之整數)。Examples of the bivalent Rf ⁰ compound (a) include the following.

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, preferably an integer from 0 to 100, but k+t is from 2 to 200, preferably from 3 to 150, and s is 0~6 integer).

(In the formula, j is independently an integer of 1~3, h and i are integers of 0~200, preferably an integer of 2~100, but h+i is 2~300, preferably 4~200, each Repeating units can be randomly bonded).

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, preferably an integer from 0 to 100, but k+t is from 2 to 200, preferably from 3 to 150, and s is 0~6 integer).

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, preferably an integer from 0 to 100, but k+t is from 2 to 200, preferably from 3 to 150, and s is 0~6 integer).

(式(9)中，Q¹ 、a及b如上述。括弧內所示之H係與Q¹ 構造中之Si原子直接鍵結之氫原子)。The compound (b) can be specifically represented by the following formula (9).

(In formula (9), Q ¹ , a, and b are as described above. H shown in parentheses is a hydrogen atom directly bonded to the Si atom in the Q ¹ structure).

(上述式中，a、b如上述)。Examples of the compound (b) include the following.

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

Particularly preferred are the following.

(上述式中，Rf⁰ 、Q¹ 、a及b如上述)。When Rf ⁰ in the compound (a) is a monovalent group, it is preferable to make the number of olefinic groups in the compound (a) relative to the number (a+b) of SiH groups in one molecule of the compound (b). Up to (a+b), preferably a quantity response. The structure of the obtained compound (c) can be represented by the following formula (10).

(In the above formula, Rf ⁰ , Q ¹ , a and b are as described above).

(式中，k為0~200之整數，較好為0~100之整數)。

(式中，k為0~200之整數，較好為0~100之整數)。Examples of the compound (c) represented by the formula (10) include the following.

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100).

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100).

(上述式中，Q¹ 、Rf⁰ 及b如上述。括弧內所示之H係與Q¹ 構造中之Si原子直接鍵結之氫原子)。When Rf ⁰ in the compound (a) is a divalent group, it is desirable to react with a molar ratio of compound (a): compound (b)=1:2, and the structure of the obtained compound (c) can be represented by the following formula (11), for example . That is, a structure in which one molecule of the compound (b) is introduced at both ends of the compound (a).

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

(式中，j獨立為1~3之整數，h、i分別為0~200之整數，較好為2~100之整數，但h+i為2~300，較好為4~200，各重複單位可以無規鍵結)。Examples of the compound (c) represented by the formula (11) include the following.

(In the formula, j is independently an integer of 1~3, h and i are integers of 0~200, preferably an integer of 2~100, but h+i is 2~300, preferably 4~200, each Repeating units can be randomly bonded).

The above-mentioned addition reaction can be carried out without a solvent, but it can also be carried out in the presence of a solvent as necessary. As the solvent, a generally widely used organic solvent such as toluene, xylene, and isooctane may be used. However, it is preferably above the reaction temperature of the boiling point system and does not hinder the reaction, and the fluorine-containing compound (c) formed after the reaction is soluble at the reaction temperature. For example, it is desirable that parts of fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether undergo fluorine modification The quality solvent is particularly preferably m-xylene hexafluoride.

The addition reaction catalyst only needs to use the conventional knowledge. For example, compounds containing platinum, rhodium or palladium can be used. Among them, a compound containing platinum is preferred. Hexachloroplatinum (IV) acid hexahydrate, platinum carbonyl vinyl methyl complex, platinum-divinyl tetramethyl disilaxane complex, platinum- Cyclovinylmethylsiloxane complex, platinum-octanal/octanol complex or platinum supported on activated carbon. The amount of catalyst should be an effective amount. In particular, for the compound (a), the amount of metal contained may be 0.1 to 5,000 mass ppm, more preferably 1 to 1,000 mass ppm.

In the addition reaction, the feeding order of each component is not particularly limited. An example is the following method: a method of slowly heating the mixture of compound (a), compound (b) and catalyst from room temperature to the addition reaction temperature, and heating the mixture of compound (a), compound (b) and diluting solvent After adding the catalyst to the target reaction temperature, adding the compound (a) to the mixture of the compound (b) heated to the target reaction temperature and the catalyst, the compound (b) heated to the target reaction temperature ) The method of adding the mixture of compound (a) and catalyst dropwise. Among them, it is particularly preferable to add a catalyst after heating the mixture of the compound (a), the compound (b) and the dilution solvent to the target reaction temperature, or dropwise add the compound (b) heated to the target reaction temperature Compound (a) and catalyst mixture method. The above addition reaction conditions may be based on conventionally known methods. In particular, it is desirable to perform the reaction in a dry environment, in air or inert gas (N ₂ , Ar, etc.) at a reaction temperature of 50 to 150°C, preferably 70 to 120°C, for 0.5 to 96 hours, preferably for 1 to 48 hours.

The compounding amount of the compound (a) is preferably less than (a+b) for the number of olefin groups possessed by the compound (a) per molecule of the compound (b) having (a+b) SiH groups. It is preferably a quantity. In particular, when Rf ⁰ of compound (a) is a divalent group, it is desirable to react with a molar ratio of compound (a): compound (b) = 1:2. In particular, in order to prevent three-dimensional crosslinking, it is desirable that the olefin group of the compound (a) and the compound (b) be subjected to an addition reaction in an excessive amount, and then the unreacted compound (b) is removed by distillation under reduced pressure.

Next, the addition reaction of the SiH group of the fluorine-containing compound (c) obtained above and the compound (d) having a terminal olefin group and an epoxy group in one molecule can obtain the fluorine-containing epoxy compound represented by the above formula (1) Modified organosilicon compound.

The compound (d) is exemplified by compounds represented by the following formulas (2a) to (5a).

In the above formula, f'is an integer from 0 to 8, e is an integer from 0 to 5, g is an integer from 0 to 10, and f'+2g+e is within the range of 2-18. Preferably, f is an integer from 0 to 6, e is 1 or 2, g is an integer from 0 to 4, and f'+2g+e is in the range of 2-8. n'is an integer of 0~18, preferably an integer of 0~13. As described above, R ^{2 is} preferably a hydrogen atom or a methyl group.

The following are exemplified as the compound (d). These compounds can be used alone or in combination of two or more.

The addition reaction conditions of the compound (c) and the compound (d) may be based on conventionally known methods. It is preferably in the presence of the above addition reaction catalyst, in a dry environment, in air or inert gas (N ₂ , Ar, etc.) at a reaction temperature of 50 to 150°C, preferably 50 to 120°C, for 0.5 to 96 Hours, preferably 1 to 48 hours. A solvent can also be used for this reaction as needed.

The compounding amount of compound (d) to compound (c) can be any value, but it is desirable to use the number of terminal olefin groups that compound (d) has equal to the number of SiH groups that compound (c) has, or the terminal The number of olefin groups becomes excessive, and after the addition reaction, the unreacted compound (d) is removed by vacuum distillation or the like. In particular, it is desirable that the ratio of the number of terminal olefin groups in the compound (d) having one SiH group in the compound (c) be 1.0 to 5.0, preferably 1.0 to 2.0.

(式中，k為0~200之整數，較好為0~100之整數)。

(式中，k為0~200之整數，較好為0~100之整數)。

(式中，k為0~200之整數，較好為0~100之整數)。

(式中，k為0~200之整數，較好為0~100之整數)。

(式中，j獨立為1~3之整數，h、i分別為0~200之整數，較好為2~100之整數，但h+i為2~300，較好為4~200，各重複單位可以無規鍵結)。

(式中，j獨立為1~3之整數，h、i分別為0~200之整數，較好為2~100之整數，但h+i為2~300，較好為4~200，各重複單位可以無規鍵結)。

(式中，j獨立為1~3之整數，h、i分別為0~200之整數，較好為2~100之整數，但h+i為2~300，較好為4~200，各重複單位可以無規鍵結)。As the compound (A) represented by the general formula (1), particularly preferred are the compounds shown below.

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100).

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100).

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100).

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100).

(In the formula, j is independently an integer of 1~3, h and i are integers of 0~200, preferably an integer of 2~100, but h+i is 2~300, preferably 4~200, each Repeating units can be randomly bonded).

(In the formula, j is independently an integer of 1~3, h and i are integers of 0~200, preferably an integer of 2~100, but h+i is 2~300, preferably 4~200, each Repeating units can be randomly bonded).

(In the formula, j is independently an integer of 1~3, h and i are integers of 0~200, preferably an integer of 2~100, but h+i is 2~300, preferably 4~200, each Repeating units can be randomly bonded).

These compounds (A) may be of a single type, or a plurality of different compounds (A) may be mixed and used.

The present invention is an active energy ray-curable composition containing the above compound (A) and at least one photopolymerization initiator (B). The photopolymerization initiator (B) is not particularly limited if it is a compound that can start the polymerization of the epoxy group of the compound (A) by irradiation with light (especially ultraviolet rays), but especially a photoacid generator, as Generally, a wide range of users can exemplify various onium salts decomposed by light.

As such the cases, for example having as the counter anion SbF _{^{6 -, AsF 6 -, BF}} 4 -, B (C 6 F 5) 4 -, PF 6 -, (Rf "") x PF 6-x ^- (In the formula, (Rf"" is independently a C 1-8 alkyl group, a C 2-8 alkenyl group, a C 6-10 aryl group, and a hydrogen atom bonded to a carbon atom of each group Allyl diazonium salt (diazonium salt), diallyl phosphonium salt (phosphonium salt), triallyl are substituted with fluorine atoms for groups above 80 mol%, x is an integer from 1 to 5) Although it is based on oxamium salt (ammonium salt), etc., from the viewpoint of toxicity, it is particularly desirable to be an onium salt having a counter anion of boron and phosphorus series.

Examples of the photopolymerization initiator (B) include those shown above, and various compounds and mixtures of these are commercially available. The specific product names are "API Co., Ltd. "CPI Series" (e.g. CPI-100P, CPI-101A8, CPI-200K, CPI-210S, CPI-310B, CPI-400PG), ADEKA Corporation "ADEKA OPTOMER SP Series” (e.g. SP150, SP152, SP170, ADEKAO SP172), Sanshin Chemical’s “SANAID SI series” (e.g. SI-60L, SI-80L, SI-100L), Fujifilm and Koko Pure Chemical Industries, Ltd. “Optical WPI” Series (for example, PI-169, WPI-170, WPI-124, WPI-116, WPI-113), BASF company "IGRACURE 250, IGRACURE 270, IGRACURE 290", etc. These can be used in combination of monomers and plural kinds. And in recent years, there are also commercially available polymerization initiators with both photo-cation generation and thermal cation generation functions, which can also be used. An example is TA-100 of SAN APRO Co., Ltd.

In the present invention, in addition to the component (A) and the component (B), the component (C) composed of one or more compounds having cationic curability other than the component (A) may be further included. Examples of the cation-hardenable compound include compounds having one or more cyclic ethers such as epoxy groups and oxetanyl groups in one molecule, compounds having a vinyl ether group, and aliphatic compounds such as isobutylene (IB). Saturated hydrocarbon compounds, styrene derivatives, lactones or cyclic carbonates and other carbonyl-containing compounds, bicyclic orthoesters, spiroorthocarbonates, spiroorthoesters, N-vinylcarbazole and other cationic polymerizable nitrogen-containing compounds (Single) etc.

Among these, the epoxy-containing compounds include aromatic epoxides, alicyclic epoxides and aliphatic epoxides.

Examples of the aromatic epoxide include monovalent or polyvalent phenol derivatives having at least one aromatic ring such as phenol, bisphenol A, bisphenol F, bisphenol AF, and glycidyl ether of phenol novolac. Furthermore, it is also possible to use a compound in which an alkyl ether or an ester structure is introduced to a part of the glycidyl ether structure.

As the alicyclic epoxide, a compound obtained by epoxidizing a compound having at least one cyclohexene ring and cyclopentene ring can also be used, and an alkyl ether or an alkyl ether oligomer is introduced into the structure as part of its structure Polymer, ester structure, ε-caprolactone oligomer compound. Specific examples include vinyl cyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, limonene dioxide, and bis(3,4 -Epoxycyclohexylmethyl)adipate, dicyclopentadiene dioxide 1,4-cyclohexanedimethanol bis(3,4-epoxycyclocarbonate), etc.

Examples of aliphatic epoxides include aliphatic polyhydric alcohols or polyglycidyl ethers of alkylene oxide adducts of these (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether) Glyceryl ether, etc.), polyglycidyl esters of aliphatic polybasic acids (diglycidyl tetrahydrophthalate, etc.), epoxides of long-chain unsaturated compounds (epoxidized polybutadiene, plant-derived Epoxides of unsaturated hydrocarbon compounds).

As the compound having an oxetanyl group, conventional ones can be used, and examples thereof include, for example, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl (3-ethyl-3-oxacyclo Butyl methyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanyl methyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanyl methyl) ether, 1,4 -Bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanyl sesquisiloxane and phenol novolac oxetane etc. Examples of specific trade names include "ARONE OXETANE series" manufactured by East Asia Synthetic Co., Ltd.

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, and phenyl vinyl ether. , P-methoxyphenyl vinyl ether and other aromatic vinyl ether. Furthermore, bifunctional vinyl ethers such as butanediol-1,4-divinyl ether, triethylene glycol divinyl ether, and dipropylene glycol divinyl ether can be cited.

As the styrene derivative, in addition to styrene, derivatives of α-methylstyrene, p-methoxystyrene, p-third butoxystyrene and the like can be exemplified.

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

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

Examples of bicyclic orthoesters are 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7 -Trioxabicyclo-[2.2.2]octane, etc.

Examples of spiro orthocarbonate are 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]dec One ethane and so on.

Among them, those having an epoxy group, an oxetanyl group, and a vinyl ether group are particularly preferred. In addition to the above-mentioned monomers, these polymerizable reactive groups can also be used in a silicone polymer (oligomer ) The shape of the end and side chain.

The ratio of each component of the active energy ray-curable composition of the present invention is determined in consideration of the nature of the cationic polymerizable compound or the type of energy ray and the amount of irradiation, temperature, curing time, humidity, coating film thickness, etc. It is particularly limited, but when only the compound having cationic curability is the component (A), the component (B) preferably contains 0.01 to 20 parts by mass, particularly preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of the (A) component. (B) When the amount of the component is too small, since the concentration of the initiator component is relatively low, it is easy to cause poor curing, and the reaction rate decreases. When there is too much, the amount of broken pieces of the initiator, which does not participate in the cross-linking structure, contained in the hardened material after hardening becomes excessive, and there may be an unexpected effect on the physical properties of the hardened material.

Furthermore, when the active energy ray-curable composition of the present invention further contains the component (C), the component (B) preferably contains 0.01 to 20 parts by mass with respect to the total of 100 parts by mass of the component (A) and the component (C). Parts, especially good contains 0.05~10 parts by mass. In this case, when the amount of the component (B) is too small, the concentration of the initiator component is relatively low, so that the curing failure is likely to occur, and the reaction rate decreases. When there is too much, the amount of broken pieces of the initiator that does not participate in the cross-linked structure contained in the hardened material after hardening becomes excessive, which may cause unexpected impact on the physical properties of the hardened material.

In addition, when the active energy ray-curable composition of the present invention contains the component (C), the component (A) preferably contains 0.01 to 10 parts by mass, particularly preferably 0.05 to 100 parts by mass of the (C) component. 5 parts by mass.

The active energy ray-curable composition of the present invention may also contain a sensitizer as needed to complement curability. As these sensitizers, for example, the sensitizers disclosed in Japanese Laid-Open Patent No. 11-279212 and Japanese Laid-open Patent No. 09-183960, etc. can be used, and specific examples include anthracene {anthracene, 9,10-dibutoxyanthracene , 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.; pyrene; 1,2-benzoanthracene; perylene; tetraacene; Coronene; thioxanthone {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropyl thioxanthone and 2,4-diethyl thioxanthone, etc.; phenothiazine {phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N-phenyl Phenothiazine, etc.; xanthene; naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene and 4-methoxy- 1-naphthol, etc.; ketones {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl -2-hydroxy-2-methylphenylacetone and 4-benzyl-4'-methyldiphenyl sulfide, etc.; carbazole {N-phenylcarbazole, N-ethylcarbazole, poly -N-vinylcarbazole and N-glycidylcarbazole, etc.; chrysene {1,4-dimethoxymethylene and 1,4-di-α-methylbenzyloxymethylene, etc.}; Phenanthrene {9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.} etc. When the sensitizer is contained, the content of the sensitizer is preferably 1 to 300 parts by mass, and more preferably 5 to 200 parts by mass relative to 100 parts by mass of the component (B).

The hardenable composition of the present invention may further contain conventional additives (pigments, fillers, antistatic agents, flame retardants, defoamers, flow regulators, light stabilizers, antioxidants, adhesiveness-imparting agents as needed) Agents, ion supplements, coloring inhibitors, solvents, non-reactive resins and oils, oligomers, etc.).

Regarding the above (B) component, (C) component and other additives that can be arbitrarily formulated, for example, "Technonet company" "Light hardening technical information manual material" (2000, TECHNONET company), Japan Photopolymer Technology Association "Photopolymer Handbook" (1989, Industrial Survey Society), Comprehensive Technology Center, "UV·EB Hardening Technology" (1982, Comprehensive Technology Center), RADTECH Research Society, "UV·EB Hardener" (1992, CMC), Technical Information Association, "Uncured UV curing, causes of obstruction and countermeasures" (2003, Technical Information Association), 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), Technical Information Association, "The Design, Characteristic Evaluation, and New Applications of UV Curing Resin" (2017, Technical Information Association), CMC Publishing, "The Market Actuality of UV·EB Hardening Materials and Products" And prospects (2007, published by CMC), Science & Technology, "Optimization of UV Hardening Process" (2008, Science & Technology), etc. have revealed many conventional knowledge, these can be used in any combination.

Furthermore, the active energy ray-curable composition of the present invention may contain a solvent as necessary. Examples of 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 acetic acid Esters such as ethyl ester and ethyl lactate, glycol ether esters of propylene glycol monomethyl ether acetate, etc. The formulation amount of the solvent is not particularly limited, but it is preferably 100 parts by mass relative to the total of the (A) component and (B) component (when the (C) component is included, it is (A), (B), (C) component A total of 100 parts by mass), preferably 20 to 900 parts by mass, especially preferably 50 to 400 parts by mass.

The method for preparing the active energy ray-curable composition of the present invention is not particularly limited. The curable composition of the present invention can be obtained by mixing the above-mentioned (A) component with (B) component, (C) component as needed, other optional additives and solvent according to a conventionally known method.

In addition, as a general use form of the active energy ray-curable composition of the present invention, if the active energy ray-curable composition layer of the present invention is cured and adhered or adhered, it can be applied to any substrate. However, examples thereof include resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, selephane, and diethylene-based fibers. Element, triethyl acetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cyclic olefin polymer, cyclic olefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, Ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluororesin, nylon, Resin such as acrylic resin. It can be used on the surface of those in any form such as a film, a plate, and a molded member.

In addition, when coating on the film substrate, it may be a structure in which the adhesive is applied on the opposite side of the coating and forming the fluorine-containing active energy ray-curable composition layer, and a release film for protecting the adhesive may also be arranged .

The aforementioned film substrate may be a substrate made only of the resin film exemplified above. However, in order to improve the adhesion to the active energy ray-curable composition of the present invention, a primer may be provided on the aforementioned resin film Thin film substrate. Examples of the undercoat layer include polyester resins, urethane resins, and acrylic resins.

In addition, the active energy ray curable composition of the present invention may be applied to a cured or uncured layer that does not correspond to the curable composition of the present invention. For example, the active energy ray-curable composition of the present invention can be repeatedly coated on a hardened material layer having higher deformation prevention properties such as hardness, durability, antistatic property, and curling.

In addition, for the purpose of improving the adhesion with the active energy ray-curable composition of the present invention, the surface of the resin film may also be subjected to surface roughening treatment, corona discharge treatment, chromic acid treatment by sandblasting, solvent treatment, etc. Flame treatment, hot air treatment, ozone/ultraviolet radiation treatment, oxidation treatment, etc.

The method for applying the active energy ray-curable composition of the present invention to the above substrate or article is not particularly limited, but for example, roll coating, gravure coating, flow coating, curtain coating, dip coating, Conventional coating methods such as spray coating, spin coating, bar coating, inkjet printing, and screen printing.

After coating, the coating film is irradiated with active energy rays to harden it. Here, any one of electron beams, ultraviolet rays and the like can be used as the active energy rays, but ultraviolet rays are particularly preferable. As the ultraviolet source, mercury lamps, metal halogen lamps, and LED lamps are preferred. As the amount of ultraviolet radiation, if it is too small, uncured components remain, and if it is too large, the coating film and the substrate may deteriorate, so it is expected to be in the range of 10 to 10,000 mJ/cm ² , particularly in the range of 100 to 4,000 mJ/cm ² .

In addition, in order to prevent hardening caused by moisture, the irradiation environment is replaced with gas such as air, nitrogen, carbon dioxide, argon, etc. whose moisture content in the gas is controlled during ultraviolet irradiation, or the surface of the coating film has mold release properties. The ultraviolet-permeable protective layer is covered, and ultraviolet rays are irradiated thereon, or when the substrate has ultraviolet-permeability, the coating film surface is covered with a mold-releasing protective layer and then irradiated with ultraviolet rays from the side opposite to the coating surface of the substrate. In addition, in order to effectively perform the leveling of the coating film or the reaction of the cationically polymerizable groups in the coating film, the coating film and the substrate may be heated by any method such as an ultraviolet ray or hot air drying furnace before and during the irradiation of the ultraviolet ray.

The thickness of the hardened layer of the active energy ray-curable composition thus obtained is not particularly limited, but it is preferably 0.01 to 5,000 μm, and particularly preferably 0.05 to 200 μm.

In addition, the hardened layer of the active energy ray-curable composition of the present invention thus obtained becomes a static value measured from the angle formed by the liquid surface and the solid surface 1 second after the 2 μL droplets of ion-exchanged water are placed on the liquid The water contact angle (also simply referred to as water contact angle) is above 100°, especially above 105°. In addition, it is preferable that the static oleic acid contact angle (also referred to as oleic acid contact angle), which is measured according to the angle formed by the liquid surface and the solid surface after 1 second of 4 μL droplets of oleic acid, is 60° or more , Especially for water and oil repellent surfaces above 65°. Furthermore, in order to achieve the above-mentioned contact angle, the cured product layer of the fluorine-containing active energy ray curable composition of the present invention is preferably such that the total surface area of the cured product layer is a layer having an average thickness of 10 nm or more. Moreover, the more unreacted cationic polymerizable groups remain on the surface of the hardened layer, the better it can be arbitrarily subjected to active energy ray hardening treatment and photopolymerization initiator (B) in a water-managed environment or under heating conditions. Adjustment of the amount of preparation and maintenance of dark reaction in a clean environment after irradiation of active energy rays, etc.

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 can form water repellent oil resistance, antifouling property, fingerprint resistance, friction resistance, and abrasion resistance on the surface of the article The hardened resin layer.

Furthermore, the present invention provides an article having a cured film obtained by applying and curing the active energy ray curable composition of the present invention on the surface. As described above, if the active energy ray-curable composition of the present invention is used, a cured film (cured resin layer) having excellent surface characteristics can be formed on the surface of a substrate (article). In particular, it can be used to impart water repellency, oil repellency, and antifouling properties to the surface of the cationic hardening hard coat layer. By this, it is possible to impart a hard-coated surface that is difficult to adhere to dirt, mechanical oil, etc. due to human oils such as fingerprints, sebum, sweat, and the like, cosmetics, etc., and has excellent wiping properties. Therefore, the active energy ray-curable composition of the present invention can provide substrates (articles) that are likely to be contaminated by human grease, cosmetics, etc. due to human contact, or human grease or mechanical oil with operators The anti-fouling coating film or protective film on the surface of the engineering material film used inside the machine with the possibility of contamination.

The hardened film (hardened resin layer) formed using the active energy ray-curable composition of the present invention is used as a portable (communication) information terminal, digital media player, etc. for tablet personal computers, notebook computers, mobile phones, smart phones, etc. Frames of various devices such as e-book readers, watch-type and glasses-type wearable computers; liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent display tubes (VFD), Field emission projection displays, CRT, toner displays, etc. various black panel displays, TV screens, etc. display operation machine surfaces and various optical films used in these, automotive exterior, piano or furniture glossy surfaces , Marble and other building stone surfaces, toilets, bathrooms, washstands and other decorative building materials that flow around, art display protection glass, display windows, display cabinets, photo frame covers, watches, car window glass, trains, It is useful for coating films and surface protective films made of transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components such as window glass of airplanes, automobile headlights, taillights, etc., and various mirror components.

Among them, various devices, such as tablet personal computers, notebook computers, smart phones, mobile phones, and other portable (communication) information terminals, are particularly used as display input devices with touch displays and the like that operate on the screen with human fingers or palms , Smart watches, digital media players, e-book readers, digital photo frames, game consoles, digital cameras, digital cameras, GPS display recorders, navigation devices for automobiles, control panels for automobiles, automatic cash claim The surface protective film of various controllers such as money saving devices, cash ATMs, vending machines, digital signage (electronic signage), security system terminals, POS terminals, remote controllers, etc., and display input devices such as panel switches for in-vehicle devices. it works.

Furthermore, the hardened film formed by the active energy ray-curable composition of the present invention is used as an optical recording medium for optical disks, optical disks, etc.; spectacle lenses, prisms, lens sheets, protective films, polarizing plates, optical filters, double Convex lenses, Fresnel lenses, anti-reflective films, various camera lenses, various lens protection filters, optical fibers, optical couplers, and other optical parts and optical device surface protection coatings are also useful.

As described above, the essence of the active energy ray-curable composition of the present invention is to impart water repellency by arranging the perfluoropolyether structure of the fluorine-containing epoxy-modified organosilicon compound (A) of the present invention on the surface of the object of interest , Oil repellency, friction, antifouling, fingerprints are not conspicuous, excellent fingerprint wiping, wear resistance, low refractive index characteristics, solvent resistance, chemical resistance and other excellent properties.

When the fluorine-containing active energy ray-curable composition of the present invention is used in this way, it is sufficient to select the proper method of use based on the conventional technology corresponding to the individual application, according to the characteristics that emphasize the combination of the formulation, composition ratio, and the like. These conventional techniques not only include fluorine-containing compositions, but also include the methods used for existing active energy ray-curable compositions and are included in the scope of review.

For example, when preparing the active energy ray-curable composition of the present invention, in addition to the fluorine-containing epoxy-modified organosilicon compound (A) of the present invention, when combining various formulations of the aforementioned curable composition, it is important to When using low-refractive-index properties or using its low-reflective properties, if you use reactive hollow silica or hollow silica without reactive groups, various polyfunctional compounds as compound (C), and improve the coating strength or scratch resistance In the case of compounding appropriate amounts of various polyfunctional compounds as compound (C), when using an epoxy-containing compound that has a slow hardening rate as compound (C), by blending an oxygen-containing heterocyclic butyl compound or The vinyl ether compound-containing compound increases the curing speed, etc., and is a method that can be easily analogized based on the knowledge that conventional cationic curing compounds are formulated. [Example]

Examples and comparative examples are shown below to explain the present invention in more detail, but the present invention is not limited to the following examples.

(式中，Rf”為下述基，重複單位數具有分佈，5.2係平均值，

) 與六氟化間-二甲苯30.0g，邊攪拌邊加熱至90℃。於其中以30分鐘滴加烯丙基縮水甘油醚8.0g與鉑/1,3-二乙烯基-四甲基二矽氧烷錯合物之甲苯溶液0.010g(以鉑換算2.49×10^-8 mol)之混合溶液，於90℃攪拌8小時。該情況下，烯丙基縮水甘油醚所具有之末端烯烴基之個數相對於上述含氟環狀矽氧烷具有之SiH基1個之比為1.02。以¹ H-NMR確認原料的Si-H消失後，進行活性碳處理。隨後減壓餾除溶劑或過量烯丙基縮水甘油醚，獲得以下述式表示之化合物(A-1) 34.2g。

[Synthesis Example 1]-Production of compound (A-1) was carried out in a dry nitrogen environment in a 100 ml three-necked flask equipped with a reflux device and a stirring device, and fed with 30.0 g of fluorinated cyclic silicone represented by the following formula :

(In the formula, Rf" is the following group, the number of repeating units has a distribution, 5.2 average

) 30.0g of m-xylene with hexafluoride, heated to 90°C with stirring. To this was added 0.010g of toluene solution of 8.0g of allyl glycidyl ether and platinum/1,3-divinyl-tetramethyldisilaxane complex (2.49×10 ^{-8 in} terms of platinum) mol) of the mixed solution was stirred at 90°C for 8 hours. In this case, the ratio of the number of terminal olefin groups possessed by the allyl glycidyl ether to one SiH group possessed by the fluorine-containing cyclic siloxane is 1.02. After confirming the disappearance of Si-H of the raw material by ¹ H-NMR, activated carbon treatment was performed. Subsequently, the solvent or excess allyl glycidyl ether was distilled off under reduced pressure to obtain 34.2 g of the compound (A-1) represented by the following formula.

與六氟化間-二甲苯700g及四甲基環四矽氧烷361g，邊攪拌邊加熱至90℃。於其中投入鉑/1,3-二乙烯基-四甲基二矽氧烷錯合物之甲苯溶液0.442g(以Pt單體計為1.1×10^-6 mol)，使內溫維持於90℃以上之狀態持續攪拌4小時。以¹ H-NMR確認原料的烯丙基消失後，減壓餾除溶劑或過量之四甲基環四矽氧烷，隨後進行活性碳處理。獲得以下述式表示之無色透明之液狀化合物(P-1) 498g。

[Synthesis Example 2]-The compound (A-2) was produced in a dry nitrogen environment, and a 2000ml three-necked flask equipped with a reflux device and a stirring device was charged with the whole having α-unsaturated bonds at both ends expressed by the following formula Fluoropolyether 500g:

700g with m-xylene hexafluoride and 361g of tetramethylcyclotetrasiloxane, heated to 90°C with stirring. 0.442 g of a toluene solution of platinum/1,3-divinyl-tetramethyldisilazane complex (1.1×10 ^-6 mol as Pt monomer) was added to maintain the internal temperature at 90°C Continue stirring for 4 hours in the above state. After confirming the disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent or excess tetramethylcyclotetrasiloxane was distilled off under reduced pressure, followed by activated carbon treatment. 498 g of a colorless and transparent liquid compound (P-1) represented by the following formula was obtained.

60.0 g of the above-mentioned compound (P-1) was mixed with 10.0 g of allyl glycidyl ether and 60.0 g of m-xylene hexafluoride, and the mixture was heated to 80° C. in a nitrogen atmosphere while stirring. In this case, the ratio of the number of terminal olefin groups possessed by the allyl glycidyl ether to one SiH group possessed by the compound (P-1) is 1.15. Put 0.021 g of platinum/1,3-divinyl-tetramethyldisilaxane complex in toluene solution (5.6×10 ^-8 mol as Pt monomer) to maintain the internal temperature at 90~ The stirring was continued for 6 hours at 120°C. After confirming the disappearance of Si-H groups of the raw materials by ¹ H-NMR, activated carbon treatment was performed. Subsequently, the solvent or excess allyl glycidyl ether was distilled off under reduced pressure to obtain 66.2 g of the compound (A-2) represented by the following formula in a translucent state.

[Synthesis Example 3] Production of compound (A-3) 60.0 g of the above compound (P-1) was mixed with 10.9 g of 3-vinylcyclohexene oxide and 60.0 g of m-xylene hexafluoride while stirring Heat to 80°C under a nitrogen atmosphere. In this case, the ratio of the number of terminal olefin groups possessed by the 3-vinylcyclohexene oxide to one SiH group possessed by the compound (P-1) is 1.14. Put 0.021 g of platinum/1,3-divinyl-tetramethyldisilaxane complex in toluene solution (5.6×10 ^-8 mol as Pt monomer) to maintain the internal temperature at 90~ The stirring was continued for 6 hours at 120°C. After confirming the disappearance of Si-H groups of the raw materials by ¹ H-NMR, activated carbon treatment was performed. Subsequently, the solvent or excess 3-vinylcyclohexene oxide was distilled off under reduced pressure to obtain 66.1 g of the compound (A-3) represented by the following formula in a translucent state.

(h’=6.8、i’=5.7、h’及i’分別為平均值) 與六氟化間-二甲苯700g及五甲基環五矽氧烷865g，邊攪拌邊加熱至90℃。於其中投入鉑/1,3-二乙烯基-四甲基二矽氧烷錯合物之甲苯溶液0.442g(以Pt單體計為1.1×10^-6 mol)，使內溫維持於90℃以上之狀態持續攪拌4小時。以¹ H-NMR確認原料的烯丙基消失後，減壓餾除溶劑或過量之五甲基環五矽氧烷，隨後進行活性碳處理。獲得以下述式表示之無色透明之液狀化合物(P-2) 538g。

(h’=6.8、i’=5.7、h’及i’分別為平均值)[Synthesis Example 4] • The compound (A-4) was produced in a dry nitrogen environment, and put into a 2000ml three-necked flask equipped with a reflux device and a stirring device, and charged with all the α-unsaturated bonds at both ends expressed by the following formula Fluoropolyether 500g:

(h'=6.8, i'=5.7, h'and i'are average values), 700g of m-xylene hexafluoride and 865g of pentamethylcyclopentasiloxane, heated to 90°C with stirring. 0.442 g of a toluene solution of platinum/1,3-divinyl-tetramethyldisilazane complex (1.1×10 ^-6 mol as Pt monomer) was added to maintain the internal temperature at 90°C Continue stirring for 4 hours in the above state. After confirming the disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent or excess pentamethylcyclopentasiloxane was distilled off under reduced pressure, followed by activated carbon treatment. 538 g of a colorless and transparent liquid compound (P-2) represented by the following formula was obtained.

(h'=6.8, i'=5.7, h'and i'are average values)

(h’=6.8、i’=5.7、h’及i’分別為平均值)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 the mixture was heated to 80° C. in a nitrogen atmosphere while stirring. In this case, the ratio of the number of terminal olefin groups possessed by the allyl glycidyl ether to one Si-H group possessed by the compound (P-2) is 1.2. Put 0.021 g of platinum/1,3-divinyl-tetramethyldisilaxane complex in toluene solution (5.6×10 ^-8 mol as Pt monomer) to maintain the internal temperature at 90~ The stirring was continued for 6 hours at 120°C. After confirming the disappearance of Si-H groups of the raw materials by ¹ H-NMR, activated carbon treatment was performed. Subsequently, the solvent or excess allyl glycidyl ether was distilled off under reduced pressure to obtain 134 g of the compound (A-4) represented by the following formula as a colorless and transparent form.

(h'=6.8, i'=5.7, h'and i'are average values)

[Examples and Comparative Examples] (Modulation of active energy ray hardening composition) Each component was mixed with the composition described in Table 1 below to prepare an active energy ray-curable composition.

B-1：光陽離子聚合起始劑CPI-200K(磷系陰離子型三芳基鏻鹽，溶劑稀釋品，SAN APRO股份有限公司製) B-2：光陽離子聚合起始劑CPI-210S(磷系陰離子型三芳基鏻鹽，粉體，SAN APRO股份有限公司製) B-3：光・熱陽離子聚合起始劑TA-100(鋶鹽，粉體，SAN APRO股份有限公司製) C-1：液狀環氧樹脂EPOTOTE ZX-1059(下述式之雙酚A、雙酚F單體混合物，新日鐵住金化學股份有限公司)

C-2：下述式之4官能環氧化合物

D-1：甲基乙基酮 D-2：乙酸丁酯

B-1: Photo-cationic polymerization initiator CPI-200K (phosphorus anionic triarylphosphonium salt, solvent diluted product, manufactured by SAN APRO Co., Ltd.) B-2: Photo-cationic polymerization initiator CPI-210S (phosphorus system) Anionic triarylphosphonium salt, powder, manufactured by SAN APRO Co., Ltd.) B-3: Light and thermal cationic polymerization initiator TA-100 (manganese salt, powder, manufactured by SAN APRO Co., Ltd.) C-1: Liquid epoxy resin EPOTOTE ZX-1059 (mixture of bisphenol A and bisphenol F monomers of the following formula, Nippon Steel & Sumitomo Chemical Co., Ltd.)

C-2: 4-functional epoxy compound of the following formula

D-1: Methyl ethyl ketone D-2: Butyl acetate

(Formation of hardened film) Each composition of Preparation Examples 1 to 14 was applied with a spin coater to a thickness of about 12 μm (wet film thickness) on a polycarbonate plate with a thickness of 2 mm, and dried with a hot air dryer. The dry film thickness after drying is about 5 μm. Subsequently, using a conveying metal halogen UV irradiation device (manufactured by Panasonic Electric Co., Ltd., 80 w/cm), ultraviolet rays of a specific accumulated light amount were irradiated under the conditions shown in Table 2 under a nitrogen atmosphere to obtain a cured cured film. In addition, each composition of Preparation Examples 6 to 8, 12 to 14 was applied to a polycarbonate plate having a thickness of about 12 μm (wet film thickness) with a spin coater, and dried with a hot air dryer. The dry film thickness after drying is about 5 μm. Subsequently, using a conveying metal halogen UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd., 80 w/cm), under the conditions shown in Table 3, a specific accumulated amount of ultraviolet rays was irradiated under a nitrogen atmosphere to obtain a cured cured film.

(Evaluation method) [Evaluation of water and oil repellency] Using a contact angle meter DropMaster (produced by Kyowa Interface Science Co., Ltd.), the contact angle of the surface of the hardened film obtained above with water (water contact angle) and with oleic acid at 25° C. (oleic acid contact angle) were measured. The measurement was carried out 30 minutes after the UV irradiation. The water contact angle was measured based on the angle formed by the liquid surface and the solid surface 1 second after the 2 μL droplets of ion-exchanged water were deposited. The oleic acid contact angle was measured from the angle formed by the liquid surface and the solid surface 1 second after the 4 μL droplet of oleic acid was deposited.

[Magic ink (non-stick)] Oil-based ink (made by ZEBRA Co., Ltd., Hi-Mckee bold) was applied to the surface of the cured product, and the non-stick property of the ink was visually evaluated using the following indicators. The measurement was carried out 45 minutes after UV irradiation. A: Fast and non-stick B: Not sticking C: It's all sticking

[Fingerprint wiping property] Five testers transferred the forehead sebum to the surface of the hardened object with their fingers, and evaluated the wipeability when wiping with BEMCOT (manufactured by Asahi Kasei Corporation) by the following evaluation criteria. The measurement is carried out 1 hour to 2 hours after UV irradiation. A: The fingerprint is easy to wipe off B: wipe off fingerprints C: The fingerprint cannot be wiped off The above evaluation results are shown in Table 2 and Table 3, respectively.

Claims (10)

An active energy ray-curable composition, which is an active energy ray-curable composition containing a fluorine-containing epoxy-modified organosilicon compound (A) represented by the following general formula (1) and a photopolymerization initiator (B) ,

(In formula (1), Rf is independently a monovalent or divalent group with a number average molecular weight of 400 to 40,000 having a fluoropolyether structure. When Rf is a monovalent group, it is represented by the following formula:

(In the above formula, j is an integer from 1 to 3, k is an integer from 0 to 200, k'is an integer from 1 to 200, l and m are integers from 1 to 100 respectively), when Rf is a divalent base, it is Expressed in the following formula:

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, but k+t is from 2 to 200, and s is an integer from 0 to 6),

(In the formula, j is independently an integer of 1~3, h and i are integers of 0~200, but h+i is 2~300, and each repeating unit can be randomly bonded),

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, but k+t is from 2 to 200, and s is an integer from 0 to 6), or

(In the formula, r is an integer from 2 to 6, k and t are integers from 0 to 200, but k+t is from 2 to 200, and s is an integer from 0 to 6). When Rf is a monovalent base, a' Is 1, a is an integer from 1 to 6, when Rf is a divalent group, a'is 2, a is 1, b is an integer from 1 to 20, a+b is an integer from 3 to 21, and Q ^{1 is} independently A group having at least (a+b) valence of (a+b) Si atoms, and expressed by the following formula:

(In the formula, a and b are as described above, the dashed line represents a bonding bond, each silicon atom having a unit shown in a repeating parenthesis is bonded to Rf in the above formula (1), and having b repeating parentheses Each silicon atom of the unit shown is bonded to Q ² in the aforementioned formula (1), the arrangement of the units shown in parentheses may be random), Q ^{2 is} independent of each other and may include an ether bond or an ester bond, and may A divalent hydrocarbon group having a ring structure of 1 to 20 carbon atoms, X is independently a group represented by the following formula (I) or (II),

(In formula (I), R ^{1 is} independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and may include an ether bond or an ester bond, and may have a cyclic structure),

(In formula (II), R ^{2 is} independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms)), the active energy ray-curable composition imparts a water contact angle of 100° to the surface Those with hardened objects above. The active energy ray-curable composition according to claim 1, wherein the structure represented by -Q ² -X- in the aforementioned formula (1) is selected from the bases represented by the following formulas (2) to (5) ,

(In the above formula, f is an integer of 1-10, e is an integer of 0-5, g is an integer of 0-10, f+2g+e is in the range of 1-20, n is an integer of 1-20, R ^{2 is} independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms). The active energy ray-hardenable composition according to claim 1 or 2, wherein in the aforementioned formula (1), Q ^{2 is} independently selected from the group represented by the following formula,

The active energy ray-curable composition according to claim 2 or 3, wherein the structure represented by -Q ² -X in the aforementioned formula (1) is the following formula,

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, a phosphonium salt, and a monium salt. The active energy ray-curable composition according to any one of claims 1 to 6, wherein the compound having cationic curability is only the component (A), the component (B) contains 0.01 relative to 100 parts by mass of the component (A) ~20 parts by mass. The active energy ray-curable composition according to any one of claims 1 to 6, which further contains (C) component composed of one or more cation-curable compounds other than (A) component, relative to ( A) The total of the component and the (C) component is 100 parts by mass, and the (B) component contains 0.01 to 20 parts by mass. The active energy ray-curable composition according to claim 8, wherein the component (C) is a compound having one or more epoxy groups, vinyl ether groups, oxetanyl groups, or carbonyl groups in each molecule, and a fat Group unsaturated hydrocarbon compounds, styrene derivatives, bicyclic orthoesters, spiroorthocarbonates, spiroorthoesters or cationically polymerizable nitrogen-containing compounds. The active energy ray-curable composition according to claim 8 or 9, wherein the component (A) contains 0.01 to 10 parts by mass relative to 100 parts by mass of the component (C), and the water contact angle of the surface of the cured product after curing is 100° the above.