JP4868150B2 - Light and thermosetting coating composition, and article having the cured film - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a solventless light and thermosetting coating composition used for paints, coatings, etc., and an article having the cured film, and more specifically, a protective film having high hardness and excellent scratch resistance. In addition, the present invention relates to a solvent-free light and thermosetting coating agent composition that provides a protective film excellent in stain resistance and an article having the cured film.

  Synthetic resins such as polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cyclic polyolefin resin, polyethylene terephthalate resin, and triacetyl cellulose resin have advantages such as light weight, transparency, and easy processability. Therefore, in recent years, such synthetic resins have been used in various fields such as optical disks such as CD and DVD, display windows such as liquid crystal and EL panels, and various functional films.

  In order to improve the scratch resistance of those surfaces, it is a common practice to form a transparent and scratch-resistant hard coat on the recording and / or reproducing beam incident side surface of the medium. The hard coat is formed by using a compound having two or more photoreactive groups such as vinyl and (meth) acrylic groups in the molecule, or an alkoxysilane having a photoreactive group such as vinyl and (meth) acrylic groups. A siloxane compound having a cage structure hydrolyzed and condensed in the presence of a basic catalyst (Japanese Patent Laid-Open Nos. 2002-363414 and 2004-143449: Patent Documents 1 and 2), an alkoxysilane having a photoreactive group, and colloidal A composition containing a reaction product of silica or the like is applied to the surface of the medium, and this is cured by irradiation with active energy rays such as ultraviolet rays. However, such a hard coat mainly employs a (meth) acryloxypropyl group as a photoreactive group, and sufficient scratch resistance cannot be obtained. Further, antifouling effect against contaminants such as fingerprint stains and wiping ability of magic ink cannot be expected.

  Examples of applying a siloxane compound containing a (meth) acryloxymethyl group as a photoreactive group as a silica-based film have been reported so far. However, in this case, it is not applied as a hard coating agent, but is flattened for the purpose of forming pores by decomposing / erasing organic groups after curing by heating, UV / EB irradiation, and plasma treatment. It is used as an interlayer insulating film having a low dielectric constant (Japanese Patent Laid-Open No. 2005-179587: Patent Document 3).

  On their surfaces, contamination by various contaminants and fingerprints occur during use. Such contamination and fingerprint attachment are not preferable, and the surface of the optical information medium may be subjected to appropriate surface treatment for improving antifouling property, reducing fingerprint adhesion, or improving fingerprint removability. is there. For example, various water and oil repellent treatments have been studied on the surface of optical information media.

  For improving the antifouling property, a siloxane compound having a cage structure obtained by hydrolytic condensation of an alkoxysilane having a polymerizable functional group and an alkoxysilane having a perfluoroalkyl group in the presence of a basic catalyst has been proposed (Patent No. 1). No. 3603133: Patent Document 4). A film obtained by curing a composition containing this compound has a high contact angle of oleic acid and is expected to improve antifouling properties. Wearability etc. will fall remarkably.

Addition of various antistatic agents has been studied for the purpose of improving antistatic properties. Reaction product of polyether-modified silicone and lithium perchlorate (JP-A-5-320625: Patent Document 5), reaction product of polyfunctional acrylic and lithium perchlorate (Patent No. 3673590: Patent Document 6), A mixture of a polyfunctional acrylate and (CF ₃ SO ₂ ) ₂ NLi (JP-A-9-278831, JP-A-2001-288325: Patent Documents 7 and 8) has been proposed, but the scratch resistance is insufficient. is there.

Therefore, a mixture of a silane hydrolyzate and (CF ₃ SO ₂ ) ₂ NLi (Japanese Patent Laid-Open Nos. 2005-146110 and 2006-70120: Patent Documents 9 and 10) is proposed for the purpose of improving scratch resistance. However, antifouling properties such as resistance to magic ink were insufficient.

JP 2002-363414 A JP 2004-143449 A Japanese Patent Application Laid-Open No. 2005-179587 Japanese Patent No. 3603133 JP-A-5-320625 Japanese Patent No. 3673590 JP-A-9-278831 JP 2001-288325 A JP-A-2005-146110 JP 2006-70120 A

  The present invention has been made in view of the above circumstances, and can form a protective film excellent in scratch resistance and crack resistance on a support substrate, and further, an antifouling effect against contaminants such as fingerprint stains, An object of the present invention is to provide a solvent-free light and thermosetting coating composition capable of imparting antistatic properties and wiping properties of magic ink, and an article having the cured film.

As a result of intensive investigations to achieve the above object, the present inventor [A] an organopolysiloxane compound represented by the following siloxane unit formula (1), [C] (CF ₃ (CF ₂ ) _m SO ₂ ) ₂ NLi (m = 0 to 7), [D] radical photopolymerization initiator and / or thermal condensation catalyst, and if necessary, contain (B) [A] component (meth) acrylic group-containing compound The film formed by curing the solvent-free light and thermosetting coating agent composition can form a protective film excellent in scratch resistance and crack resistance on the supporting substrate, and further, fingerprint stains, etc. The present inventors have found that the antifouling effect against the pollutants of the above, the wiping property of the magic ink, and the antistatic property can be imparted, and the present invention has been made.

［式中、Ｘは水素原子又は炭素数１〜４のアルキル基であり、Ｒ¹〜Ｒ⁶は置換基を有してもよい炭素数１〜６の一価脂肪族炭化水素基又は炭素数６〜１０の一価芳香族炭化水素基であり、上記置換基はフェニル基、フッ素原子、塩素原子、臭素原子、（メタ）アクリロキシ基、エポキシ構造含有基、メルカプト基、イソシアネート基、アミノ官能性基、パーフルオロアルキル基、ポリ（ヘキサフルオロプロピレンオキサイド）構造含有基からなる群から選択される１種又は２種以上の一価有機基である。但し、Ｒ¹〜Ｒ⁶のいずれかに、下記式（２）
ＣＨ₂＝Ｃ（Ｒ⁷）ＣＯＯＣＨ₂− （２）
（式中、Ｒ⁷は水素原子又はメチル基である。）
で表される基を１個以上含み、総シロキサン単位に対して前記式（２）で表される有機基が置換しているシロキサン単位が２０〜９９．９ｍｏｌ％であり、更にＲ¹〜Ｒ⁶のいずれかに、置換基としてパーフルオロアルキル基又はポリ（ヘキサフルオロプロピレンオキサイド）構造含有基を有する炭素数１〜６の一価脂肪族炭化水素基を１個以上含み、総シロキサン単位に対して該炭化水素基が置換しているシロキサン単位が０．１〜５０ｍｏｌ％である。ａは平均０≦ａ＜０．４であり、ｂは平均０≦ｂ＜０．５であり、ｃは平均０＜ｃ≦１であり、ｄは平均０≦ｄ＜０．４であり、ｅは平均０≦ｅ＜０．２であり、ａ＋ｂ＋ｃ＋ｄ＝１である。］
で表されるオルガノポリシロキサン化合物：
［Ａ］成分と［Ｂ］成分の合計１００質量部に対して２０〜１００質量部、
［Ｂ］［Ａ］成分以外の（メタ）アクリル基含有化合物：
［Ａ］成分と［Ｂ］成分の合計１００質量部に対して０〜８０質量部、
［Ｃ］（ＣＦ₃（ＣＦ₂）_mＳＯ₂）₂ＮＬｉ（但し、ｍ＝０〜７である。）：
［Ａ］成分と［Ｂ］成分の合計１００質量部に対して０．５〜１５質量部、
［Ｄ］ラジカル系光重合開始剤及び／又は熱縮合触媒：
［Ａ］成分と［Ｂ］成分の合計１００質量部に対して０．１〜２０質量部
を含有してなる無溶剤かつ室温にて液状であることを特徴とする光及び熱硬化性コーティング剤組成物。
〔２〕シロキサン単位式（１）のＲ¹〜Ｒ⁶において、式（２）で表される有機基含有シロキサン単位の含有率をＡｍｏｌ％、下記式（３）
ＣＨ₂＝Ｃ（Ｒ⁸）ＣＯＯＣ₃Ｈ₆− （３）
（式中、Ｒ⁸は水素原子又はメチル基である。）
で表される有機基含有シロキサン単位の含有率をＢｍｏｌ％とすると、
０．５＜Ａ／（Ａ＋Ｂ）≦１
であることを特徴とする〔１〕記載のコーティング剤組成物。
〔３〕オルガノポリシロキサン化合物の重量平均分子量が１，０００〜５，０００である〔１〕又は〔２〕記載のコーティング剤組成物。
〔４〕オルガノポリシロキサン化合物のシラノール基含有量が０〜２質量％である〔１〕〜〔３〕のいずれかに記載のコーティング剤組成物。
〔５〕オルガノポリシロキサン化合物中に含まれる不揮発分が９９質量％以上である〔１〕〜〔４〕のいずれかに記載のコーティング剤組成物。
〔６〕オルガノポリシロキサン化合物が、総シロキサン単位に対し、ポリ（ヘキサフルオロプロピレンオキサイド）構造含有基が置換しているシロキサン単位が０．１〜２０ｍｏｌ％である〔１〕〜〔５〕のいずれかに記載のコーティング剤組成物。
〔７〕オルガノポリシロキサン化合物が、総シロキサン単位に対し、ジメチルシロキサン単位が１〜１０ｍｏｌ％である〔１〕〜〔６〕のいずれかに記載のコーティング剤組成物。
〔８〕［Ｃ］成分が、（ＣＦ₃ＳＯ₂）₂ＮＬｉである〔１〕〜〔７〕のいずれかに記載のコーティング剤組成物。
〔９〕〔１〕〜〔８〕のいずれかに記載のコーティング剤組成物の硬化皮膜が形成されてなる物品。
なお、本発明において、無溶剤とは、本発明の硬化条件で硬化することのない非反応性で、本発明のシリコーン樹脂を溶解する溶剤を含まないことを意味する。 Accordingly, the present invention provides the following light and thermosetting coating agent compositions and articles having the cured film.
[1] [A] The following siloxane unit formula (1)

[Wherein, X is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{1 to} R ⁶ are monovalent aliphatic hydrocarbon groups or carbon atoms having 1 to 6 carbon atoms which may have a substituent. 6-10 monovalent aromatic hydrocarbon groups, the above substituents being phenyl group, fluorine atom, chlorine atom, bromine atom, (meth) acryloxy group, epoxy structure-containing group, mercapto group, isocyanate group, amino functionality A monovalent organic group selected from the group consisting of a group, a perfluoroalkyl group, and a poly (hexafluoropropylene oxide) structure-containing group. However, in any of R ^{1 to} R ⁶ , the following formula (2)
^{_{CH 2 = C (R 7)}} COOCH 2 - (2)
(In the formula, R ⁷ is a hydrogen atom or a methyl group.)
The siloxane unit containing at least one group represented by formula (2) and substituted with the organic group represented by the formula (2) with respect to the total siloxane unit is 20 to 99.9 mol%, and further R ^{1 to} R ⁶ includes one or more monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms having a perfluoroalkyl group or a poly (hexafluoropropylene oxide) structure-containing group as a substituent, and based on the total siloxane units The siloxane unit substituted by the hydrocarbon group is 0.1 to 50 mol%. a is average 0 ≦ a <0.4, b is average 0 ≦ b <0.5, c is average 0 <c ≦ 1, d is average 0 ≦ d <0.4, e has an average of 0 ≦ e <0.2 and a + b + c + d = 1. ]
Organopolysiloxane compound represented by:
20 to 100 parts by mass with respect to 100 parts by mass in total of the [A] component and the [B] component,
[B] (Meth) acrylic group-containing compound other than [A] component:
0 to 80 parts by mass with respect to 100 parts by mass in total of [A] component and [B] component,
[C] (CF ₃ (CF ₂ ) _m SO ₂ ) ₂ NLi (where m = 0 to 7):
0.5 to 15 parts by mass with respect to 100 parts by mass in total of the [A] component and the [B] component,
[D] radical photopolymerization initiator and / or thermal condensation catalyst:
A light and thermosetting coating agent characterized by being solvent-free and liquid at room temperature, containing 0.1 to 20 parts by mass with respect to 100 parts by mass of the total of [A] component and [B] component Composition.
[2] In R ^{1 to} R ⁶ of the siloxane unit formula (1), the content of the organic group-containing siloxane unit represented by the formula (2) is represented by Amol%, the following formula (3)
^{_{CH 2 = C (R 8)}} COOC 3 H 6 - (3)
(In the formula, R ⁸ is a hydrogen atom or a methyl group.)
When the content of the organic group-containing siloxane unit represented by
0.5 <A / (A + B) ≦ 1
[1] The coating composition according to [1].
[3] The coating agent composition according to [1] or [2], wherein the organopolysiloxane compound has a weight average molecular weight of 1,000 to 5,000.
[4] The coating agent composition according to any one of [1] to [3], wherein the silanol group content of the organopolysiloxane compound is 0 to 2% by mass.
[5] The coating agent composition according to any one of [1] to [4], wherein a non-volatile content contained in the organopolysiloxane compound is 99% by mass or more.
[6] Any of [1] to [5], wherein the organopolysiloxane compound has 0.1 to 20 mol% of siloxane units substituted with a poly (hexafluoropropylene oxide) structure-containing group with respect to the total siloxane units. A coating agent composition according to claim 1.
[7] The coating agent composition according to any one of [1] to [6], wherein the organopolysiloxane compound is 1 to 10 mol% of dimethylsiloxane units with respect to the total siloxane units.
[8] The coating agent composition according to any one of [1] to [7], wherein the [C] component is (CF ₃ SO ₂ ) ₂ NLi.
[9] An article formed with a cured film of the coating composition according to any one of [1] to [8].
In the present invention, the term “solvent-free” means non-reactive that does not cure under the curing conditions of the present invention and does not include a solvent that dissolves the silicone resin of the present invention.

The light and thermosetting coating composition of the present invention uses a photoreactive group-containing organopolysiloxane compound whose main component is a siloxane unit containing an acryloxymethyl group, so that the distance between cross-linking points of the cured resin can be reduced. As the length becomes shorter, the crosslink density also increases, thereby improving the wear resistance and heat resistance of the resulting cured film. Further, by mixing (CF ₃ (CF ₂ ) _m SO ₂ ) ₂ NLi, antistatic properties can be obtained without impairing these characteristics.

The light and thermosetting coating composition of the present invention comprises:
[A] a photoreactive group-containing organopolysiloxane compound described later,
[C] (CF ₃ (CF ₂ ) _m SO ₂ ) ₂ NLi (where m = 0 to 7),
[D] radical photopolymerization initiator and / or thermal condensation catalyst,
In addition, it contains a (meth) acrylic group-containing compound other than the components [B] and [A] as required, and is characterized by being solvent-free and liquid at room temperature.

［式中、Ｘは水素原子又は炭素数１〜４のアルキル基であり、Ｒ¹〜Ｒ⁶は置換基を有してもよい炭素数１〜６の一価脂肪族炭化水素基又は炭素数６〜１０の一価芳香族炭化水素基であり、上記置換基はフェニル基、フッ素原子、塩素原子、臭素原子、（メタ）アクリロキシ基、エポキシ構造含有基、メルカプト基、イソシアネート基、アミノ官能性基、パーフルオロアルキル基、ポリ（ヘキサフルオロプロピレンオキサイド）構造含有基からなる群から選択される１種又は２種以上の一価有機基である。但し、Ｒ¹〜Ｒ⁶のいずれかに、下記式（２）
ＣＨ₂＝Ｃ（Ｒ⁷）ＣＯＯＣＨ₂− （２）
（式中、Ｒ⁷は水素原子又はメチル基である。）
で表される基を１個以上含み、総シロキサン単位に対して前記式（２）で表される有機基が置換しているシロキサン単位が２０〜９９．９ｍｏｌ％であり、更にＲ¹〜Ｒ⁶のいずれかに、置換基としてパーフルオロアルキル基又はポリ（ヘキサフルオロプロピレンオキサイド）構造含有基を有する炭素数１〜６の一価脂肪族炭化水素基を１個以上含み、総シロキサン単位に対して該炭化水素基が置換しているシロキサン単位が０．１〜５０ｍｏｌ％である。ａは平均０≦ａ＜０．４であり、ｂは平均０≦ｂ＜０．５であり、ｃは平均０＜ｃ≦１であり、ｄは平均０≦ｄ＜０．４であり、ｅは平均０≦ｅ＜０．２であり、ａ＋ｂ＋ｃ＋ｄ＝１である。］ [A] Organopolysiloxane Compound The photoreactive group-containing organopolysiloxane compound in the present invention is used as a main component of a solventless light and thermosetting coating agent composition, and has the following siloxane unit formula (1): It is represented by

[Wherein, X is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{1 to} R ⁶ are monovalent aliphatic hydrocarbon groups or carbon atoms having 1 to 6 carbon atoms which may have a substituent. 6-10 monovalent aromatic hydrocarbon groups, the above substituents being phenyl group, fluorine atom, chlorine atom, bromine atom, (meth) acryloxy group, epoxy structure-containing group, mercapto group, isocyanate group, amino functionality A monovalent organic group selected from the group consisting of a group, a perfluoroalkyl group, and a poly (hexafluoropropylene oxide) structure-containing group. However, in any of R ^{1 to} R ⁶ , the following formula (2)
^{_{CH 2 = C (R 7)}} COOCH 2 - (2)
(In the formula, R ⁷ is a hydrogen atom or a methyl group.)
The siloxane unit containing at least one group represented by formula (2) and substituted with the organic group represented by the formula (2) with respect to the total siloxane unit is 20 to 99.9 mol%, and further R ^{1 to} R ⁶ includes one or more monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms having a perfluoroalkyl group or a poly (hexafluoropropylene oxide) structure-containing group as a substituent, and based on the total siloxane units The siloxane unit substituted by the hydrocarbon group is 0.1 to 50 mol%. a is average 0 ≦ a <0.4, b is average 0 ≦ b <0.5, c is average 0 <c ≦ 1, d is average 0 ≦ d <0.4, e has an average of 0 ≦ e <0.2 and a + b + c + d = 1. ]

In this siloxane unit formula (1), a, b, and d may be 0 in this organopolysiloxane compound.
(R ⁶ SiO _3/2 ) _c (OX) _e ,
(R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (OX) _e ,
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁶ SiO _3/2 ) _c (OX) _e ,
(R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (OX) _e ,
(R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (OX) _e ,
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (OX) _e ,
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (OX) _e
There is. Since e is a positive number of 0 or less than 0.2, when (e = 0), (OX) _e is deleted from the above equation, and when e> 0, the above equation is obtained.
This silicone resin is a branched, reticulated, three-dimensional organopolysiloxane resin composed of these siloxane units, and has (meth) acryloxy groups and silanol groups. Cures rapidly by irradiation with high energy rays such as heat.

  a, b, c and d mean the average number of moles of each siloxane unit when the total number of moles of each siloxane unit is 1, and each siloxane unit is contained in an average number of moles per molecule. It shows that. Therefore, a + b + c + d = 1. Moreover, e has shown how many mol% of the siloxane unit which the hydrolyzable group couple | bonded on the silicon is contained in D-Q siloxane unit on average. Therefore, 0 ≦ e <(b + c + d).

Since the molecular weight generally decreases when M units (R ¹ R ² R ³ SiO _1/2 ) are introduced into the organopolysiloxane resin, the range (a) is an average of 0 ≦ a <0.4, preferably an average. 0 ≦ a <0.2. When the D unit (R ⁴ R ⁵ SiO _2/2 ) is introduced, the degree of branching of the resin decreases, the modulus of the cured product decreases, and crack resistance and antifouling properties are improved. Mean 0 ≦ b <0.5, preferably 0 <b <0.02. When the T unit (R ⁶ SiO _3/2 ) is introduced, the degree of branching is generally improved, the modulus of the cured product is increased, and the wear resistance is improved. Therefore, c is an average of 0 <c ≦ 1, The average is preferably 0.8 ≦ c ≦ 1. When Q unit (SiO _4/2 ) is introduced, generally the degree of branching of the resin is remarkably improved, the modulus of the cured product is remarkably increased, and the crack resistance is lowered, so d is an average of 0 ≦ d < 0.4, preferably d = 0. When a siloxane unit containing a hydrolyzable group is introduced, the hardness improvement due to thermal condensation increases, but on the other hand, a reactive group remains in the resin and storage stability decreases, so e is an average. 0 ≦ e <0.2, preferably 0 ≦ e <0.1 on average.

Among the siloxane unit formula (1), among R ^{1 to} R ⁶ which are substituents bonded to a silicon atom, the monovalent aliphatic hydrocarbon group which may have a substituent having 1 to 6 carbon atoms is as follows: Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl group, tolyl group, phenylethyl group, xylyl group, and naphthyl group. Substituents include phenyl group, fluorine atom, chlorine atom, bromine atom, (meth) acryloxy group, epoxy structure-containing group, mercapto group, isocyanate group, amino functional group, perfluoroalkyl group, poly (hexafluoropropylene oxide) ) Structure-containing groups.

Among these, the following formula (2)
^{_{CH 2 = C (R 7)}} COOCH 2 - (2)
(In the formula, R ⁷ is a hydrogen atom or a methyl group.)
At least one of R ^{1 to} R ⁶ is included (that is, at least one of the organic groups bonded to the silicon atom of the silicone resin is a group of the above formula (2)). ). R ⁷ is preferably a hydrogen atom in consideration of curability when irradiated with high energy rays such as ultraviolet rays. It is preferable that the siloxane unit which the organic group represented by Formula (2) substitutes with respect to a total siloxane unit is 20-99.9 mol%, More preferably, it is 50-99.9 mol%.

  As for the hydrolyzable group bonded to the silicon atom, X is a hydrogen atom or carbon such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group. It is a C1-C4 alkyl group, Preferably they are a hydrogen atom and a methyl group, More preferably, it is a hydrogen atom.

Among the siloxane unit formula (1), among R ^{1 to} R ⁶ which are substituents bonded to a silicon atom, the photoreactive group is an organic group represented by the formula (2), or high energy such as ultraviolet rays. Considering the curability during irradiation, the formula (3)
^{_{CH 2 = C (R 8)}} COOC 3 H 6 - (3)
(In the formula, R ⁸ is a hydrogen atom or a methyl group.)
The organic group represented by these is mentioned. R ⁸ is preferably a hydrogen atom in consideration of curability when irradiated with high energy rays such as ultraviolet rays.

Here, when the content of the organic group-containing siloxane unit of the formula (2) is Amol% and the content of the organic group-containing siloxane unit of the formula (3) is Bmol%, 0.5 <A / (A + B) ≦ 1 is preferable, and 0.75 ≦ A / (A + B) ≦ 1 is more preferable. If the content is outside the above range, the crosslinking density, which is the effect of the present invention, is not sufficiently increased, and sufficient wear resistance may not be obtained.
In addition, 0-35 mol% is preferable with respect to the total siloxane unit, and, more preferably, the siloxane unit which the organic group represented by the said Formula (3) substitutes is 0-23 mol%.

  In the siloxane unit formula (1), for the purpose of improving the antifouling effect, it is preferable that the siloxane unit substituted with the fluorine-containing organic group is 0.1 to 50 mol% with respect to the total siloxane units, and more Preferably it is 1-5 mol%. If it is less than 0.1 mol%, the antifouling property may not be obtained, and if it exceeds 50 mol%, sufficient wear resistance cannot be obtained. Specific examples of the fluorine-containing organic group include an organic group containing a C 1-20 perfluoroalkyl group or an organic group containing a poly (hexafluoropropylene oxide) structure.

More specific structures of the organic group containing a perfluoroalkyl group having 1 to 20 carbon atoms and the organic group containing a poly (hexafluoropropylene oxide) structure include CF ₃ C ₂ H ₄ —, C ₄ F _{9 C 2 H 4 -, C} 8 F 17 C 2 H 4 -, C 8 F 17 C 3 H 6 -, C 3 F 7 OC (CF 3) FCF 2 OC (CF 3) FCH 2 OC 3 H 6 - _{, C 3 F 7 OC (CF} 3) FCF 2 OC (CF 3) FC (= O) NHC 3 H 6 -, F (C (CF 3) FCF 2 O) 6 C (CF 3) FC (= O) _{NHC 3 H 6 -, C 3} F 7 O (C 3 F 6 O) r C 2 F 4 CH 2 CH 2 (r = 2~100) and the like.

Among these, in particular, including a siloxane unit substituted with an organic group containing a poly (hexafluoropropylene oxide) structure can provide a sufficient antifouling effect, and (CF ₃ (CF ₂ ) _m SO ₂ ) ₂ NLi (provided that m = 0 to 7) is improved or antistatic properties are improved. In this case, the siloxane unit substituted by the poly (hexafluoropropylene oxide) structure-containing group is preferably 0.1 to 20 mol%, particularly 1 to 5 mol%, based on the total siloxane units.

  In the siloxane unit formula (1), for the purpose of improving the magic ink resistance, the content of dimethylsiloxane units is preferably 1 to 10 mol%, more preferably 0.1 to 0.1%, based on the total siloxane units. 3 mol%. When the content is less than the above-mentioned content, sufficient magic ink resistance cannot be obtained, and when the content is large, sufficient abrasion resistance may not be obtained.

  In addition to the siloxane unit S-1 in which the organic group represented by the formula (2) is substituted in this way, the silicone resin is a siloxane unit S-2 in which the organic group of the formula (3) is substituted. When the poly (hexafluoropropylene oxide) structure-containing group includes any substituted siloxane unit S-3 or dimethylsiloxane unit S-4, the organic group represented by the formula (2) is substituted. The siloxane unit S-1 is 35 to 99.8 mol%, particularly 70 to 98.9 mol%.

As the photoreactive group-containing organopolysiloxane compound, specifically, an organo comprising (Me ₂ SiO _2/2 ), (A1SiO _3/2 ), (HFPO3SiO _3/2 ) and (O _1/2 H) units. A polysiloxane compound, an organopolysiloxane compound comprising (Me ₂ SiO _2/2 ), (A1SiO _3/2 ), (C ₈ F ₁₇ C ₂ H ₄ SiO _3/2 ) and (O _1/2 H) units, Organopolysiloxane compounds comprising (A1SiO _3/2 ), (C ₈ F ₁₇ C ₂ H ₄ SiO _3/2 ) and (O _1/2 H) units, (A1SiO _3/2 ), (HFPO ₃ SiO _3/2 ) And an organopolysiloxane compound comprising (O _1/2 H) units [wherein Me is a methyl group, A1 is an acryloxymethyl group, A2 is a 3-acryloxypropyl group, HFPO3 is C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH Organic group represented by ₂ OC ₃ H ₆ —] is exemplified, but is not limited thereto.

  The weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of the organopolysiloxane compound represented by the siloxane unit formula (1) of the present invention is preferably 1,000 to 5,000, more preferably. Is 1,200 to 3,000. If it is less than 1,000, condensation is insufficient, storage stability is poor, unreacted siloxane units remain, and repelling or the like may occur on the coating surface. When it is larger than 5,000, the viscosity becomes high and handling may be difficult.

  Moreover, it is preferable that silanol group content of the obtained organopolysiloxane compound is 2 mass% or less, More preferably, it is 1 mass% or less. If it exceeds 2% by mass, a problem may occur in storage stability and the like.

Furthermore, the obtained organopolysiloxane compound preferably has a non-volatile content of 99% by mass or more such as an organic solvent.
Moreover, when the said organopolysiloxane compound is liquid at room temperature (25 degreeC), it is preferable that the viscosity measured with a rotational viscometer is 1,500-3,000 mPa * s.

[B] (Meth) acrylic group-containing compound other than [A] component In addition to the organopolysiloxane compound of [A] component, the coating agent composition of the present invention can be used as a reactive diluent as required. Functional (meth) acrylates can be included. In the case of containing no polyfunctional (meth) acrylate and having no solvent, the organopolysiloxane compound is solidified (crystallized) or has a high viscosity, which makes it difficult to produce stably, and also allows coating on a substrate. It can be very difficult.

  The polyfunctional (meth) acrylate is a main component of the curable component and forms a matrix of a film obtained after curing. The polyfunctional (meth) acrylate is a compound having two or more (meth) acryl groups in the molecule. For example, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene Oxide-modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, 3- (meth) acryloyloxyglycerin mono (meth) acrylate, urethane acrylate, epoxy acrylate, ester acrylate, etc., but are not necessarily limited to these. Not shall. These compounds may use only 1 type and may use 2 or more types together.

  The blending amount of the component [B] is 0 to 80 parts by mass, preferably 0 to 50 parts by mass, out of a total of 100 parts by mass of the component [A] and the component [B]. [B] When there are too many components, sufficient abrasion resistance cannot be obtained.

[C] (CF ₃ (CF ₂ ) _m SO ₂ ) ₂ NLi
In the present invention, (CF ₃ (CF ₂ ) _m SO ₂ ) ₂ NLi (where m = 0 to 7) is used as an antistatic agent having good compatibility and solubility. The surface resistivity of the cured product is 10 ¹⁶ Ω / □ or less at the initial stage and at high temperature and high humidity, and a sufficient dust adhesion preventing effect is obtained. When m exceeds 7, compatibility and solubility are deteriorated. Preferred is (CF ₃ SO ₂ ) ₂ NLi with m = 0.

  [C] The compounding quantity of a component is 0.5-15 mass parts with respect to a total of 100 mass parts of a [A] component and a [B] component, Preferably it is 1-10 mass parts. If the amount is less than 0.5 parts by mass, the antistatic effect cannot be obtained. If the amount exceeds 15 parts by mass, bleeding tends to occur at high temperature and high humidity, and the antifouling property and the like deteriorate.

[D] Radical photopolymerization initiator and / or thermal condensation catalyst As the curing catalyst used in the present invention, a radical photopolymerization initiator and / or a thermal condensation catalyst can be used.
The radical photopolymerization initiator can be selected from ordinary ones such as acetophenone, benzoin, benzophenone, and thioxanthone. For example, Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907 (all manufactured by Ciba Specialty Chemicals) and the like can be mentioned.

  As the thermal condensation catalyst, it can be appropriately selected from known ones. Specific examples of the thermal condensation catalyst used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, sodium formate, n-hexylamine, tributylamine, diazabicycloundecene, etc. Basic compounds such as tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, cobalt octylate, cobalt acetylacetonate, zinc octylate, Metal-containing compounds such as zinc acetylacetonate, iron acetylacetonate, tin acetylacetonate, dibutyltin octylate, dibutyltin laurate, p-toluenesulfonic acid, tri Lol acidic compounds such as acetic acid, and the like.

  The compounding quantity of a curing catalyst is 0.1-20 mass parts with respect to a total of 100 mass parts of [A] component and [B] component. A preferable compounding amount is 0.5 to 10 parts by mass, and if it is less than 0.1 part by mass, the curability is deteriorated, and if it is more than 20 parts by mass, the surface hardness is lowered.

  The coating agent composition of the present invention further comprises metal oxide fine particles, silane coupling agent, non-polymerizable diluent solvent, polymerization inhibitor, antioxidant, ultraviolet absorber, light stabilizer, antifoam, if necessary. An agent, a leveling agent, and the like may be included as long as the object of the present invention is not impaired.

  Examples of the metal oxide fine particles include oxide fine particles such as Si, Ti, Al, Zn, Zr, In, Sn, and Sb, or composite oxide particles thereof. Moreover, you may use what coat | covered the surface with silica, an alumina, etc. Specific examples of the metal oxide fine particles include fine particles of silica, alumina, zirconia, titania and the like, and silica fine particles are preferable. By adding such metal oxide fine particles, characteristics such as wear resistance can be further enhanced.

Further, the silica fine particles may be hollow or porous which is expected to have an effect such as a low refractive index.
Among the silica fine particles, those having a surface modified with a hydrolyzable silane compound having an active energy ray reactive group are preferably used. Such reactive silica fine particles undergo a crosslinking reaction by irradiation with active energy rays when the hard coat is cured, and are fixed in the polymer matrix. In addition, it is preferable that the compounding quantity of a metal oxide fine particle is 0.1-50 mass parts with respect to a total of 100 mass parts of an [A] component and a [B] component.

  The coating agent composition of this invention can be prepared by mixing the said component according to a conventional method. The obtained coating agent composition is a solvent-free liquid at room temperature, and preferably has a viscosity at 25 ° C. of 10 to 2,000 mPa · s as measured by a rotational viscometer.

  The coating agent composition of the present invention is a surface of an optical information medium such as a read-only optical disc, an optical recording disc, a magneto-optical recording disc, etc. These are applied to the surface of the reproduction beam incident surface and the surface of various display elements such as an optical lens, an optical filter, an antireflection film, a liquid crystal display, a CRT display, a plasma display, an EL display, etc. Surface scratch resistance, crack resistance, antifouling effect against contaminants such as fingerprint stains and wiping ability of magic ink can be imparted. Articles with this cured coating have antifouling properties and lubricity. It can be excellent in scratch resistance and abrasion resistance as well as excellent.

As a method for forming a film of the coating composition, the film can be produced by a spin coating method or the like.
The film thickness of the formed film is preferably in the range of 0.1 to 50 μm, particularly 0.5 to 30 μm. If the film thickness is too thin, the wear resistance may decrease, and if it is too thick, the crack resistance may decrease.

As a light source for photocuring the coating composition, a light source containing light having a wavelength in the range of 200 to 450 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, or the like is used. be able to. Although the irradiation amount is not particularly limited, 10~5,000mJ / cm ^2, it is particularly preferably 20 to 1,000 mJ / cm ^2. The curing time is usually 0.5 second to 2 minutes, preferably 1 second to 1 minute.

  For heat curing of the coating agent composition, it is preferable to treat for 1 to 120 minutes in a temperature range of 30 to 250 ° C., particularly from the viewpoint of achieving both shortening of the curing time and prevention of deterioration of the substrate. Heat treatment is preferably performed at a temperature.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
In the following examples, the volatile content was measured according to JIS C 2133, the refractive index was measured according to JIS K 0062, the OH amount was measured according to JIS K 0070, and the weight average molecular weight was measured by GPC (gel permeation chromatography). , HLC-8220 manufactured by Tosoh Corporation) and measured using THF (tetrahydrofuran) as a developing solvent.

For the magic ink resistance, a line was drawn on the cured film with a commercially available oil-based magic ink, and the wiping property when wiping with a waste cloth was visually observed.
The antifouling property was measured using a contact angle meter (CA-X150 type, manufactured by Kyowa Interface Science) for the water contact angle and the oleic acid contact angle (the larger the contact angle, the better the antifouling property).
Scratch resistance and abrasion resistance are in accordance with ASTM D 1044, and the cured film is tested for abrasion using a Taber abrasion tester (using a wear wheel CS-10F). The turbidity of the cured film before and after the abrasion test is turbid. Measured using a spectrophotometer (NHD2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the value of [turbidity after abrasion test−turbidity before abrasion test] was ΔHaze (when ΔHaze is 15 or less, scratch resistance, Wear resistance is good).
The surface resistivity is a high resistance resistivity meter (Hiresta UP MCP-HT450 type, manufactured by Dia Instruments Co., Ltd.), and the half-life is measured using a charged charge attenuation meter (Static Honest Meter, manufactured by Sicid Electrostatic Co., Ltd.) All were measured in an atmosphere of 25 ° C. and 50% RH.

［Ａｃ１：アクリロキシメチル、Ｍｅ：メチル］
を有する光反応性基含有オルガノポリシロキサン化合物であることを確認した。 [Synthesis Example 1]
As a starting material for the synthesis of an acryloxymethyl group and a fluorine-containing organopolysiloxane compound , 199.6 parts by mass (0.96 mol) of acryloxymethyltrimethoxysilane and C ₈ F ₁₇ C ₂ H ₄ Si (OCH ₃ ) ₃ were used. 17.0 parts by mass (0.03 mol), 0.9 parts by mass (0.0008 mol) of permethyldodecasiloxane (hereinafter referred to as MD-10) and 612.7 parts by mass of isopropyl alcohol were blended in a reactor, When it became uniform, 13.9 parts by mass of a 20% by mass tetramethylammonium hydroxide methanol solution, and 97.0 parts by mass of water (6.04 mol of water) twice as much as the alkoxy group were added. Stir for hours. Toluene was added, washed with water and neutralized, and then alcohol, toluene and the like were distilled off.
The obtained reaction product was liquid at 25 ° C. and had a volatile content of 0.3%, a refractive index of 1.4732, an OH amount of 0.5 mass%, and a weight average molecular weight of 1,800. From the results of infrared absorption analysis and nuclear magnetic resonance analysis, this reaction product undergoes hydrolysis condensation as ideal, and the following siloxane unit formula

[Ac1: Acryloxymethyl, Me: Methyl]
It was confirmed that the photoreactive group-containing organopolysiloxane compound had

[Example 1]
80 parts by mass of the compound obtained in Synthesis Example 1, 20 parts by mass of 1,6-hexanediol diacrylate which is a bifunctional acrylate, 7.5 parts by mass of (CF ₃ SO ₂ ) ₂ NLi and Darocur 1173 (radical initiator , Manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) 5 parts by mass, mixed with a liquid composition at 25 ° C. so as to have a thickness of 5 μm without containing the obtained solvent, and lighted with an 80 W high-pressure mercury lamp. Was irradiated for 2 seconds (accumulated dose 200 mJ / cm ² ) and cured.
In the Taber abrasion resistance test (500 g load, 100 rotations) of the obtained coating film, ΔHaze was 6, indicating good abrasion resistance. Further, the magic ink resistance was acceptable, the water contact angle was 95 °, and the oleic acid contact angle was 64 °, showing excellent antifouling properties. Further, the surface resistivity was as low as 5 × 10 ¹³ Ω / □, and the half-life was as short as 1 min.

［Ａｃ１：アクリロキシメチル、ＨＦＰＯ３：Ｃ₃Ｆ₇ＯＣ（ＣＦ₃）ＦＣＦ₂ＯＣ（ＣＦ₃）ＦＣＨ₂ＯＣ₃Ｈ₆−、Ｍｅ：メチル］
を有する光反応性基含有オルガノポリシロキサン樹脂であることを確認した。 [Synthesis Example 2]
As a starting material for the synthesis of an acryloxymethyl group and a fluorine-containing organopolysiloxane compound , 199.6 parts by mass (0.96 mol) of acryloxymethyltrimethoxysilane, HFPO3Si (OMe) ₃ [HFPO3: C ₃ F ₇ OC (CF ₃ ) 19.3 parts by mass (0.03 mol) of FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H _6- , Me: methyl], 0.9 part by mass (0.0008 mol) of MD-10, isopropyl alcohol Was mixed in a reactor of 612.7 parts by mass, and when it became uniform, 13.9 parts by mass of a 20% by mass tetramethylammonium hydroxide methanol solution, 97.0 parts by mass of water twice the mol of alkoxy groups (6.04 mol of water) was added and stirred at 25 ° C. for 12 hours. Toluene was added, washed with water and neutralized, and then alcohol, toluene and the like were distilled off.
The obtained reaction product was liquid at 25 ° C., volatile matter 0.2%, refractive index 1.4715, OH content 0.3% by mass, and weight average molecular weight 1,700. From the results of infrared absorption analysis and nuclear magnetic resonance analysis, this reaction product undergoes hydrolysis condensation as ideal, and the following siloxane unit formula

[Ac1: _{acryloxymethyl, HFPO3: C 3 F 7 OC} (CF 3) FCF 2 OC (CF 3) FCH 2 OC 3 H 6 -, Me: methyl]
It was confirmed that the photoreactive group-containing organopolysiloxane resin had

[Example 2]
80 parts by mass of the compound obtained in Synthesis Example 2, 20 parts by mass of 1,6-hexanediol diacrylate which is a bifunctional acrylate, 7.5 parts by mass of (CF ₃ SO ₂ ) ₂ NLi and Darocur 1173 (radical initiator , Manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) 5 parts by mass, mixed with a liquid composition at 25 ° C. so as to have a thickness of 5 μm without containing the obtained solvent, and lighted with an 80 W high-pressure mercury lamp. Was irradiated for 2 seconds (accumulated dose 200 mJ / cm ² ) and cured.
In the Taber abrasion test (500 g load, 100 revolutions) of the obtained coating, ΔHaze was 7, indicating good abrasion resistance. Further, the magic ink resistance was acceptable, and the water contact angle was 96 ° and the oleic acid contact angle was 61 °, showing excellent antifouling properties. Further, the surface resistivity was as low as 5 × 10 ¹² Ω / □, and the half-life was as short as 1 min.

［Ａｃ１：アクリロキシメチル、ＨＦＰＯ３：Ｃ₃Ｆ₇ＯＣ（ＣＦ₃）ＦＣＦ₂ＯＣ（ＣＦ₃）ＦＣＨ₂ＯＣ₃Ｈ₆−、Ｍｅ：メチル］
を有する光反応性基含有オルガノポリシロキサン樹脂であることを確認した。 [Synthesis Example 3]
As a starting material for the synthesis of an acryloxymethyl group and a fluorine-containing organopolysiloxane compound , 199.8 parts by mass (0.97 mol) of acryloxymethyltrimethoxysilane, HFPO3Si (OMe) ₃ [HFPO3: C ₃ F ₇ OC (CF ₃ ) 19.3 parts by mass (0.03 mol) of FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H _6- , Me: methyl] and 608.5 parts by mass of isopropyl alcohol were uniformly mixed. Then, 13.8 parts by mass of a 20% by mass tetramethylammonium hydroxide methanol solution and 97.0 parts by mass of water (6.04 mol of water) with respect to the alkoxy group were added, and the mixture was added at 25 ° C. for 12 hours. Stir. Toluene was added, washed with water and neutralized, and then alcohol, toluene and the like were distilled off.
The obtained reaction product was liquid at 25 ° C., volatile matter 0.3%, refractive index 1.4722, OH content 1.1% by mass, and weight average molecular weight 1,600. From the results of infrared absorption analysis and nuclear magnetic resonance analysis, this reaction product undergoes hydrolysis condensation as ideal, and the following siloxane unit formula

[Ac1: _{acryloxymethyl, HFPO3: C 3 F 7 OC} (CF 3) FCF 2 OC (CF 3) FCH 2 OC 3 H 6 -, Me: methyl]
It was confirmed that the photoreactive group-containing organopolysiloxane resin had

[Example 3]
80 parts by mass of the compound obtained in Synthesis Example 3, 20 parts by mass of 1,6-hexanediol diacrylate which is a bifunctional acrylate, 7.5 parts by mass of (CF ₃ SO ₂ ) ₂ NLi and Darocur 1173 (radical initiator , Manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) 5 parts by mass, mixed with a liquid composition at 25 ° C. so as to have a thickness of 5 μm without containing the obtained solvent, and lighted with an 80 W high-pressure mercury lamp. Was irradiated for 2 seconds (accumulated dose 200 mJ / cm ² ) and cured.
In the Taber abrasion resistance test (500 g load, 100 revolutions) of the obtained coating, ΔHaze was 9 indicating good abrasion resistance, and the magic ink resistance was acceptable. Further, the water contact angle was 94 ° and the oleic acid contact angle was 54 °, showing good antifouling properties. Further, the surface resistivity was as low as 5 × 10 ¹³ Ω / □, and the half-life was as short as 2 min.

[Comparative Example 1]
80 parts by mass of the compound obtained in Synthesis Example 2, 20 parts by mass of 1,6-hexanediol diacrylate which is a bifunctional acrylate, and 5 parts by mass of Darocur 1173 (radical initiator, manufactured by Ciba Specialty Chemicals, Inc.) The mixture was mixed, and the composition, which did not contain the obtained solvent, was applied to the polycarbonate at a temperature of 25 ° C. to a thickness of 5 μm, and irradiated with light with an 80 W high-pressure mercury lamp for 2 seconds (integrated dose 200 mJ / cm ² ). And cured.
In the Taber abrasion test (500 g load, 100 revolutions) of the obtained coating, ΔHaze was 7, indicating good abrasion resistance. Further, the magic ink resistance was acceptable, and the water contact angle was 96 ° and the oleic acid contact angle was 61 °, showing excellent antifouling properties. However, the surface resistivity was as high as 1 × 10 ¹⁵ Ω / □ or more, and the half-life was 60 min or more.

[Comparative Synthesis Example 1]
As a starting material for the synthesis of an acryloxymethyl group-containing organopolysiloxane compound , 206.0 parts by mass (1.00 mol) of acryloxymethyltrimethoxysilane and 539.7 parts by mass of isopropyl alcohol were blended uniformly in a reactor. Then, 12.6 parts by mass of a 20% by mass tetramethylammonium hydroxide methanol solution, 108.8 parts by mass of water (6.04 mol of water) twice as much as the alkoxy group were added, and the mixture was added at 25 ° C. for 12 hours. Stir. Toluene was added, washed with water and neutralized, and then alcohol, toluene and the like were distilled off.
The obtained reaction product had a volatile content of 0.7%, a refractive index of 1.4882, an OH amount of 1.0% by mass, and a weight average molecular weight of 1,500. This reaction product is solid at 25 ° C., and hydrolytic condensation proceeds as ideal from the results of infrared absorption light analysis and nuclear magnetic resonance analysis. The following siloxane unit formula [Ac1SiO _3/2 ] _1.0 [OH] _0.07
[Ac1: Acryloxymethyl]
It was confirmed that the photoreactive group-containing organopolysiloxane resin had

[Comparative Example 2]
50 parts by mass of the compound obtained in Comparative Synthesis Example 1, 50 parts by mass of 1,6-hexanediol diacrylate as a bifunctional acrylate, 7.5 parts by mass of (CF ₃ SO ₂ ) ₂ NLi and Darocur 1173 (radical initiation 5 parts by weight of a chemical, manufactured by Ciba Specialty Chemicals Co., Ltd., mixed with a liquid composition at 25 ° C. so as to have a thickness of 5 μm at 25 ° C. It was irradiated with light for 2 seconds (accumulated dose 200 mJ / cm ² ) and cured.
In the Taber abrasion test (500 g load, 100 revolutions) of the obtained film, ΔHaze is 5 and excellent wear resistance, the surface resistivity is as low as 1 × 10 ¹⁴ Ω / □, and the half-life is also 1 min. It was short. However, the water contact angle was 77 °, the oleic acid contact angle was not measurable, the magic ink resistance was rejected, and the antifouling property was not obtained.

［Ａｃ２：アクリロキシプロピル、ＨＦＰＯ３：Ｃ₃Ｆ₇ＯＣ（ＣＦ₃）ＦＣＦ₂ＯＣ（ＣＦ₃）ＦＣＨ₂ＯＣ₃Ｈ₆−、Ｍｅ：メチル］
を有する光反応性基含有オルガノポリシロキサン樹脂であることを確認した。 [Comparative Synthesis Example 2]
As a starting material for the synthesis of the 3-acryloxypropyl group and fluorine-containing organopolysiloxane compound , 224.6 parts by mass (0.96 mol) of 3-acryloxypropyltrimethoxysilane, HFPO3Si (OMe) ₃ [HFPO3: C ₃ F _{7 OC (CF 3) FCF 2} OC (CF 3) FCH 2 OC 3 H 6 -] 19.3 parts by weight (0.03 mol), a MD-10 0.9 parts by weight (0.0008 mol), isopropyl alcohol Was mixed in a reactor of 612.7 parts by mass, and when it became uniform, 13.9 parts by mass of a 20% by mass tetramethylammonium hydroxide methanol solution, 97.0 parts by mass of water twice the mol of alkoxy groups (6.04 mol of water) was added and stirred at 25 ° C. for 12 hours. Toluene was added, washed with water and neutralized, and then alcohol, toluene and the like were distilled off.
The obtained reaction product was liquid at 25 ° C., volatile matter 0.5%, refractive index 1.4829, OH content 0.6% by mass, and weight average molecular weight 3,000. From the results of infrared absorption analysis and nuclear magnetic resonance analysis, this reaction product undergoes hydrolysis condensation as ideal, and the following siloxane unit formula

[Ac2: _{acryloxypropyl, HFPO3: C 3 F 7 OC} (CF 3) FCF 2 OC (CF 3) FCH 2 OC 3 H 6 -, Me: methyl]
It was confirmed that the photoreactive group-containing organopolysiloxane resin had

[Comparative Example 3]
80 parts by mass of the compound obtained in Comparative Synthesis Example 2, 20 parts by mass of 1,6-hexanediol diacrylate which is a bifunctional acrylate, 7.5 parts by mass of (CF ₃ SO ₂ ) ₂ NLi and Darocur 1173 (radical initiator , Manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) 5 parts by mass, mixed with a liquid composition at 25 ° C. so as to have a thickness of 5 μm without containing the solvent, and lighted with an 80 W high-pressure mercury lamp. Was irradiated for 2 seconds (accumulated dose 200 mJ / cm ² ) and cured.
The obtained coating film passed the anti-magic ink property and exhibited a sufficient antifouling property with a water contact angle of 101 ° and an oleic acid contact angle of 64 °. Further, the surface resistivity was as low as 1 × 10 ¹⁴ Ω / □, and the half-life was as short as 2 min. However, in the Taber abrasion test (500 g load, 100 revolutions), ΔHaze was 18 and the abrasion resistance was insufficient.

Claims (9)

[A] The following siloxane unit formula (1)

[Wherein, X is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{1 to} R ⁶ are monovalent aliphatic hydrocarbon groups or carbon atoms having 1 to 6 carbon atoms which may have a substituent. 6-10 monovalent aromatic hydrocarbon groups, the above substituents being phenyl group, fluorine atom, chlorine atom, bromine atom, (meth) acryloxy group, epoxy structure-containing group, mercapto group, isocyanate group, amino functionality A monovalent organic group selected from the group consisting of a group, a perfluoroalkyl group, and a poly (hexafluoropropylene oxide) structure-containing group. However, in any of R ^{1 to} R ⁶ , the following formula (2)
^{_{CH 2 = C (R 7)}} COOCH 2 - (2)
(In the formula, R ⁷ is a hydrogen atom or a methyl group.)
The siloxane unit containing at least one group represented by formula (2) and substituted with the organic group represented by the formula (2) with respect to the total siloxane unit is 20 to 99.9 mol%, and further R ^{1 to} R ⁶ includes one or more monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms having a perfluoroalkyl group or a poly (hexafluoropropylene oxide) structure-containing group as a substituent, and based on the total siloxane units The siloxane unit substituted by the hydrocarbon group is 0.1 to 50 mol%. a is average 0 ≦ a <0.4, b is average 0 ≦ b <0.5, c is average 0 <c ≦ 1, d is average 0 ≦ d <0.4, e has an average of 0 ≦ e <0.2 and a + b + c + d = 1. ]
Organopolysiloxane compound represented by:
20 to 100 parts by mass with respect to 100 parts by mass in total of the [A] component and the [B] component,
[B] (Meth) acrylic group-containing compound other than [A] component:
0 to 80 parts by mass with respect to 100 parts by mass in total of [A] component and [B] component,
[C] (CF ₃ (CF ₂ ) _m SO ₂ ) ₂ NLi (where m = 0 to 7):
0.5 to 15 parts by mass with respect to 100 parts by mass in total of the [A] component and the [B] component,
[D] radical photopolymerization initiator and / or thermal condensation catalyst:
A light and thermosetting coating agent characterized by being solvent-free and liquid at room temperature, containing 0.1 to 20 parts by mass with respect to 100 parts by mass of the total of [A] component and [B] component Composition. In R ^{1 to} R ⁶ of the siloxane unit formula (1), the content of the organic group-containing siloxane unit represented by the formula (2) is represented by Amol%, the following formula (3)
^{_{CH 2 = C (R 8)}} COOC 3 H 6 - (3)
(In the formula, R ⁸ is a hydrogen atom or a methyl group.)
When the content of the organic group-containing siloxane unit represented by
0.5 <A / (A + B) ≦ 1
The coating agent composition according to claim 1, wherein   The coating agent composition according to claim 1 or 2, wherein the organopolysiloxane compound has a weight average molecular weight of 1,000 to 5,000.   The coating composition according to any one of claims 1 to 3, wherein the silanol group content of the organopolysiloxane compound is 2% by mass or less.   The coating agent composition according to any one of claims 1 to 4, wherein a non-volatile content contained in the organopolysiloxane compound is 99% by mass or more.   The organopolysiloxane compound is 0.1 to 20 mol% of siloxane units substituted with a poly (hexafluoropropylene oxide) structure-containing group with respect to the total siloxane units. Coating agent composition.   The coating composition according to any one of claims 1 to 6, wherein the organopolysiloxane compound has 1 to 10 mol% of dimethylsiloxane units based on the total siloxane units. The coating agent composition according to any one of claims 1 to 7, wherein the component [C] is (CF ₃ SO ₂ ) ₂ NLi.   The article | item formed by the cured film of the coating agent composition of any one of Claims 1-8 formed.