JP5678901B2 - Curable resin composition, cured product thereof and article having cured film - Google Patents

Description

  The present invention relates to a curable resin composition curable by light and / or heat and an article having a cured molded product or a cured film thereof, and more particularly, as a single molded product, which is excellent in both hardness and toughness, and is resistant to cracking. The present invention relates to a curable resin composition that provides a protective film with high hardness and excellent scratch resistance when it is used as a coating film, in addition to excellent properties, and also provides a protective film with excellent stain resistance.

  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 represented by transparent conductive films for touch panels. Yes.

  However, the resin materials represented by the above have problems in lack of heat resistance, linear expansion coefficient, birefringence, etc. when used as a film substrate for touch panels, and transparent conductive films using the substrate film The same problem was inevitable. On the other hand, high heat-resistant polymers such as polyimide, polyethersulfone, polyetherketone, polyarylate, and liquid crystal polymer are generally excellent in heat resistance, chemical resistance, and electrical insulation, but are easily colored and are used in the optical field. Is limited.

  Among these, in Japanese Patent Nos. 4256756 and 4409597 (Patent Documents 1 and 2), a polyorganosilsesquiz having a siloxane unit having a polymerizable group typified by an acrylic group as a main structural unit. Techniques relating to oxane and a resin composition using this mixed with a resin are disclosed. Further, in Patent Document 2, when a polyfunctional acrylic having an alicyclic structure is used as a second essential component to obtain a cured molded product, parameters such as linear expansion coefficient and birefringence are effective for a touch panel member. Disclosed is a technique that can be modified to various physical properties.

  On the other hand, in addition to the applied technology as the molded product, in order to improve the scratch resistance of the surface of the non-silicone (siloxane) molded product represented by the above, it is a transparent and scratch-resistant silicone (siloxane) hard coat. Is generally formed on the recording and / or reproducing beam incident surface of the medium. The hard coat is formed by using a compound having two or more photoreactive groups such as a vinyl group or a (meth) acryl group in the molecule, an alkoxysilane having a photoreactive group such as a vinyl group or a (meth) acryl group. A siloxane compound having a cage structure hydrolyzed and condensed in the presence of a basic catalyst (Japanese Patent Laid-Open No. 2002-363414, Japanese Patent No. 4400571: Patent Documents 3 and 4), alkoxysilane having a photoreactive group and colloidal silica A composition containing a reactant or the like is applied to the surface of the medium, and this is cured by irradiation with an active energy ray such as ultraviolet rays. However, such a hard coat employs a (meth) acryloxypropyl group and a (meth) acryloxymethyl group as photoreactive groups, and although a certain hardness can be obtained by the balance of the functional group amount, Instead, distortion due to curing shrinkage was large, and crack resistance and molding stability were insufficient when the film thickness was increased. The warpage of the molded product due to the same curing shrinkage is not improved in Patent Documents 1 and 2 described above.

  Examples of applying a siloxane compound containing a (meth) acryl 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 Application Laid-Open No. 2005-179587: Patent Document 5).

  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 6). 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.

Japanese Patent No. 4256756 Japanese Patent No. 44099797 JP 2002-363414 A Japanese Patent No. 4400751 Japanese Patent Application Laid-Open No. 2005-179587 Japanese Patent No. 3603133

  The present invention has been made in view of the above circumstances, and as a molded product, the balance between hardness and toughness is excellent, and as a result, a protective film excellent in scratch resistance and crack resistance can be formed on a support substrate. An object is to provide an article having a curable resin composition, a cured molded product thereof, and a cured film.

  As a result of intensive investigations to achieve the above object, the present inventors have found that a curable resin composition curable with light and / or heat containing a silicone resin represented by the following siloxane unit formula (1): When it is a single molded product, it can be excellent in both hardness and toughness, and can be excellent in crack resistance, and when it is used as a coating film, it can be a protective film with high hardness and excellent scratch resistance. The headline and the present invention were made.

［式中、Ｘは独立に水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ¹〜Ｒ⁶は独立に置換基を有してもよい炭素原子数１〜１０の一価炭化水素基であり、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、シリル基から選択される１種又は２種以上の一価有機基である。但し、Ｒ¹〜Ｒ⁶のいずれかに式（２）
ＣＨ₂＝Ｃ（Ｒ⁷）ＣＯＯ（ＣＨ₂）_n− （２）
（式中、Ｒ⁷は水素原子又はメチル基であり、ｎは４以上の整数である。）
で表される有機基を１個以上含み、総シロキサン単位に対し式（２）で表される有機基が置換しているシロキサン単位が２０〜１００ｍｏｌ％であり、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。］
で表されるシリコーン樹脂、及び多官能（メタ）アクリル化合物を含むことを特徴とする硬化性樹脂組成物。
〔２〕
式（２）で表される有機基のｎが８であることを特徴とする〔１〕記載の樹脂組成物。
〔３〕
前記シリコーン樹脂の重量平均分子量が２，０００〜１０，０００である〔１〕又は〔２〕記載の樹脂組成物。
〔４〕
前記シリコーン樹脂のシラノール基含有量が２質量％以下である〔１〕〜〔３〕のいずれかに記載の樹脂組成物。
〔５〕
前記シリコーン樹脂中に含まれる揮発分が１質量％未満である〔１〕〜〔４〕のいずれかに記載の樹脂組成物。
〔６〕
無溶剤であり、且つ室温にて液状であることを特徴とする〔１〕〜〔５〕のいずれかに記載の樹脂組成物。
〔７〕
前記シリコーン樹脂が、総シロキサン単位に対し、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）構造含有基が置換しているシロキサン単位を０．１〜２０ｍｏｌ％含有する〔１〕〜〔６〕のいずれかに記載の樹脂組成物。
〔８〕
更に、金属酸化物微粒子を含むことを特徴とする〔１〕〜〔７〕のいずれかに記載の樹脂組成物。
〔９〕
更に、光硬化触媒、ラジカル重合触媒、熱縮合触媒のいずれか１種以上の触媒を含有してなることを特徴とする〔１〕〜〔８〕のいずれかに記載の樹脂組成物。
〔１０〕
〔１〕〜〔９〕のいずれかに記載の樹脂組成物を硬化して得られる成形品。
〔１１〕
〔１〕〜〔９〕のいずれかに記載の樹脂組成物からなるコーティング剤。
〔１２〕
〔１１〕記載のコーティング剤の硬化皮膜が形成されてなる物品。
Therefore, this invention provides the resin composition shown below, the hardening molded article, and the articles | goods which have the cured film.
[1]
The following siloxane unit formula (1)

[Wherein, X is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{1 to} R ⁶ are independently monovalent hydrocarbons having 1 to 10 carbon atoms which may have a substituent. The above substituents are phenyl, fluorine, chlorine, bromine, (meth) acryloxy, epoxy structure-containing, mercapto, isocyanate, amino functional, perfluoroalkyl, poly (hexa). Fluoropropylene oxide) is a monovalent organic group selected from a structure-containing group and a silyl group. However, in any one of R ^{1 to} R ⁶ , the formula (2)
^{_{CH 2 = C (R 7)}} COO (CH 2) n - (2)
(In the formula, R ⁷ is a hydrogen atom or a methyl group, and n is an integer of 4 or more.)
The siloxane units substituted by the organic group represented by the formula (2) with respect to the total siloxane units are 20 to 100 mol%, and a is an average of 0 ≦ a <0. .4, b is on average 0 ≦ b <0.5, c is on average 0 <c ≦ 1, d is on average 0 ≦ d <0.4, and e is on average 0 ≦ e <0 .2 and a + b + c + d = 1. ]
The curable resin composition characterized by including the silicone resin represented by these , and a polyfunctional (meth) acryl compound .
[2]
N of the organic group represented by Formula (2) is 8, The resin composition as described in [1] characterized by the above-mentioned.
[3]
The resin composition according to [1] or [2], wherein the silicone resin has a weight average molecular weight of 2,000 to 10,000.
[4]
Resin composition in any one of [1]-[3] whose silanol group content of the said silicone resin is 2 mass% or less.
[5]
The resin composition according to any one of [1] to [4], wherein a volatile component contained in the silicone resin is less than 1% by mass.
[6]
The resin composition according to any one of [1] to [5], which is solvent-free and is liquid at room temperature.
[7]
[1] to [6], wherein the silicone resin contains 0.1 to 20 mol% of a siloxane unit substituted with a perfluoroalkyl group or a poly (hexafluoropropylene oxide) structure-containing group with respect to the total siloxane units. The resin composition in any one.
[ 8 ]
Furthermore, the metal oxide fine particle is contained, The resin composition in any one of [1]-[ 7 ] characterized by the above-mentioned.
[ 9 ]
Furthermore, the resin composition according to any one of [1] to [ 8 ], further comprising at least one of a photocuring catalyst, a radical polymerization catalyst, and a thermal condensation catalyst.
[10]
[1] A molded product obtained by curing the resin composition according to any one of [ 9 ].
[11]
[1] A coating agent comprising the resin composition according to any one of [ 9 ].
[12]
[ 11 ] An article formed with a cured film of the coating agent according to [ 11 ].

  The curable resin composition curable with light and / or heat of the present invention is a silicone having a siloxane unit containing a (meth) acryloxy group containing 4 or more, more preferably 8 alkylene linking groups. By using the resin as the main component, the distance between cross-linking points of the cured resin is increased, so that the cross-linking density is reduced and the curing shrinkage is eased, while the conventional alkylene linking group having 3 carbon atoms is used. Since the activity of the polymerizable group is improved as compared with the conventional silicone resin, the degree of polymerization of the film is high, and the hardness of the film obtained is high.

［式中、Ｘは独立に水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ¹〜Ｒ⁶は独立に置換基を有してもよい炭素原子数１〜１０の一価炭化水素基であり、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、シリル基から選択される１種又は２種以上の一価有機基である。但し、Ｒ¹〜Ｒ⁶のいずれかに式（２）
ＣＨ₂＝Ｃ（Ｒ⁷）ＣＯＯ（ＣＨ₂）_n− （２）
（式中、Ｒ⁷は水素原子又はメチル基であり、ｎは４以上の整数である。）
で表される有機基を１個以上含み、総シロキサン単位に対し式（２）で表される有機基が置換しているシロキサン単位が２０〜１００ｍｏｌ％であり、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。］ Hereinafter, the present invention will be specifically described.
The silicone resin used as the main component of the curable resin composition of the present invention is represented by the following siloxane unit formula (1).

[Wherein, X is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{1 to} R ⁶ are independently monovalent hydrocarbons having 1 to 10 carbon atoms which may have a substituent. The above substituents are phenyl, fluorine, chlorine, bromine, (meth) acryloxy, epoxy structure-containing, mercapto, isocyanate, amino functional, perfluoroalkyl, poly (hexa). Fluoropropylene oxide) is a monovalent organic group selected from a structure-containing group and a silyl group. However, in any one of R ^{1 to} R ⁶ , the formula (2)
^{_{CH 2 = C (R 7)}} COO (CH 2) n - (2)
(In the formula, R ⁷ is a hydrogen atom or a methyl group, and n is an integer of 4 or more.)
The siloxane units substituted by the organic group represented by the formula (2) with respect to the total siloxane units are 20 to 100 mol%, and a is an average of 0 ≦ a <0. .4, b is on average 0 ≦ b <0.5, c is on average 0 <c ≦ 1, d is on average 0 ≦ d <0.4, and e is on average 0 ≦ e <0 .2 and a + b + c + d = 1. ]

  The monovalent hydrocarbon group having 1 to 10 carbon atoms is a monovalent aliphatic hydrocarbon group such as a linear, branched or cyclic alkyl group or alkenyl group, a monovalent hydrocarbon group such as an aryl group or an aralkyl group. An aromatic hydrocarbon group is mentioned. In this case, the number of carbon atoms of 1 to 10 is the number of carbon atoms of the monovalent aliphatic hydrocarbon group or monovalent aromatic hydrocarbon group itself, and does not include the number of carbon atoms of the substituent.

In the silicone resin constituting the resin composition, a, b, and d in the siloxane unit formula (1) can be 0.
(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 ,
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (OX) _e
Is exemplified. 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 a (meth) acryloxy group. Cures rapidly by energy beam irradiation or 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 how many mol% of each siloxane unit is contained in one molecule on average. Is shown. Therefore, a + b + c + d = 1. E is a hydrolyzable group on the silicon atom in the total siloxane unit of D unit (R ⁴ R ⁵ SiO _2/2 ), T unit (R ⁶ SiO _3/2 ) and Q unit (SiO _4/2 ). It shows how many mol% of siloxane units bonded with is contained on average. Therefore, 0 ≦ e <(b + c + d).

When M units (R ¹ R ² R ³ SiO _1/2 ) are introduced into the organopolysiloxane resin, the molecular weight generally decreases, so the range is 0 ≦ a <0.4 on average, preferably 0 ≦ a <0.2. When the D unit (R ⁴ R ⁵ SiO _2/2 ) is introduced, the degree of branching of the resin is reduced, the modulus of the cured product is lowered, and crack resistance and antifouling properties are improved. ≦ b <0.5, preferably 0 <b <0.02 on average. In particular, those having dimethylsiloxane units introduced have excellent magic ink wiping properties. Therefore, when magic ink wiping properties are required, introduction of dimethylsiloxane units is preferred. 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, the average 0 <c ≦ 1, preferably Is 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 R ^{1 to} R ⁶ which are groups bonded to a silicon atom in the siloxane unit formula (1), the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms includes a methyl group, an ethyl group, and a propyl group. Butyl group, pentyl group, hexyl group, cyclohexyl group and the like. 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) Examples include a structure-containing group and a silyl group.

Among these, the formula (2)
^{_{CH 2 = C (R 7)}} COO (CH 2) n - (2)
(In the formula, R ⁷ is a hydrogen atom or a methyl group, and n is an integer of 4 or more.)
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)). ).
In the organic group represented by the above formula (2), n is an integer of 4 or more, preferably an integer of 5 to 12, and more preferably 8. R ⁷ is preferably a hydrogen atom in consideration of curability when irradiated with high energy rays such as ultraviolet rays.
The siloxane unit substituted by the organic group represented by the formula (2) is 20 mol% or more with respect to the total siloxane units, but preferably 35 to 80 mol%. When the amount of the siloxane unit substituted by the organic group represented by the formula (2) is less than 20 mol%, the photocurability is insufficient, and the flexibility of the molded product is also insufficient.

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)}} COO (CH 2) m - (3)
(In the formula, R ⁸ is a hydrogen atom or a methyl group, and m is 1 or 3.)
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%, 0.1 ≦ A / (A + B) ≦ 1, preferably 0.2 ≦ A / (A + B) ≦ 1. If the content is outside the above range, the balance between imparting flexibility of the molded product due to the reduction in crosslink density, which is an effect of the present invention, and improving the hardness of the molded product due to high activity of the polymerizable group may be impaired.
In addition, 0-80 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 0-65 mol%.

  In the siloxane unit formula (1), it is preferable to contain a siloxane unit substituted with a fluorine-containing organic group for the purpose of improving the antifouling effect. By introducing a fluorine-containing organic group, the antifouling effect against contaminants such as fingerprint stains is remarkably improved. Specific examples of the fluorine-containing organic group include an organic group containing a perfluoroalkyl group having 1 to 20 carbon atoms or an organic group containing a poly (hexafluoropropylene oxide) structure.

As a more specific structure of an organic group containing a perfluoroalkyl group having 1 to 20 carbon atoms and an organic group containing a poly (hexafluoropropylene oxide) structure,
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)
Etc.

Among these, it is more preferable that a siloxane unit substituted with an organic group containing a poly (hexafluoropropylene oxide) structure is included because a sufficient antifouling effect can be obtained. As poly (hexafluoropropylene oxide) structure,
C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H _6- ,
F (C (CF ₃ ) FCF ₂ O) ₆ C (CF ₃ ) FC (═O) NHC ₃ H ₆ −
Is particularly preferred.
In this case, it is preferable that the siloxane unit which the poly (hexafluoropropylene oxide) structure containing group substitutes is 0.1-20 mol% with respect to a total siloxane unit, 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 20 mol%, sufficient wear resistance cannot be obtained.

  In the siloxane unit formula (1), for the purpose of improving the magic ink resistance, the content of dimethylsiloxane units is preferably 0.1 to 10 mol%, more preferably 0. 1 to 3 mol%. When the content is less than the above-mentioned content, sufficient magic ink resistance may not be obtained, and when the content is large, sufficient wear 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 preferably 20 to 99.8 mol% based on the total siloxane units.

  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 an alkyl group having 1 to 4 atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

In the siloxane unit formula (1), the hydrolyzable silane monomer as a precursor raw material is not particularly limited as long as it has one or more hydrolyzable silyl groups in the molecule. Those containing a hydrolyzable silyl group having three decomposable groups are essential. For example, in the case where the molecule has two or more hydrolyzable silyl groups, among the R ^{1 to} R ⁶ , the substituent has a silyl group. When the silyl group as a substituent is a hydrolyzable silyl group, the corresponding siloxane unit is included in the unit formula (1) at the same time.

  Examples of the hydrolyzable silane monomer having two or more hydrolyzable silyl groups include 1,2-bistrimethoxysilylethane, 1,2-bistriethoxysilylethane, 1,2-bis (methyldimethoxysilyl) ethane, 1,2-bis (methyldiethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,6-bis (triethoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane, , 8-bis (triethoxysilyl) octane, 1,19-bis (trimethoxysilylethyl) -permethyldecasiloxane, N, N-bis (trimethoxysilylpropyl) amine, tris- (trimethoxysilylpropyl) isocyanate Examples include nurate.

The silicone resin used in the present invention can be produced by a known method.
For example, alkoxysilanes having functional groups such as (meth) acryloxy group-containing alkoxysilanes, perfluoroalkyl group-containing alkoxysilanes, alkylalkoxysilanes such as methylalkoxysilane, ethylalkoxysilane, etc. Hydrolyzable silane monomer is hydrolyzed in the presence of a basic catalyst with more water (more than 0.5 mol of water per 1 mol of hydrolyzable groups) than the amount that hydrolyzes all hydrolyzable groups. Thus, a (meth) acryloxy group-containing organopolysiloxane resin (silicone resin represented by the formula (1)) can be obtained.

Here, examples of the basic catalyst include sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide and the like. Among these, tetraalkylammonium hydroxide is preferable.
The addition amount of the basic catalyst is preferably 0.1 to 20% by mass, particularly 1 to 10% by mass of the blended hydrolyzable silane monomer.

  The amount of water used for the hydrolytic condensation may be larger than the amount necessary for hydrolytic condensation of all the alkoxy groups of the blended hydrolyzable silane monomer, and with respect to 1 mol of hydrolyzable groups in the blend composition, 0.55 to 10 mol of water is preferable, and 0.6 to 5 mol is particularly preferable. If the amount of water is too small, hydrolysis and condensation of the hydrolyzable group will not proceed, and if it is too much, condensation will not proceed easily. In either case, unreacted silane monomer will easily remain and repelling will occur on the surface of the film. There are things to do.

  The hydrolysis condensation reaction is preferably performed in an alcohol, and examples of the alcohol used include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol.

The above-mentioned hydrolyzable silane monomer, alcohol and basic catalyst are blended, and water is added to proceed with hydrolytic condensation. The reaction temperature at this time is usually 0 ° C. to 200 ° C., preferably 0 ° C. to 50 ° C.
After hydrolytic condensation, neutralize with acid or neutralize by washing with water, and then distill off alcohol, etc. to remove (meth) acryloxy group-containing organo, which is substantially free of solvents A polysiloxane resin can be obtained.

Specific examples of the (meth) acryloxy group-containing organopolysiloxane resin (silicone resin represented by the formula (1)) include (Me ₂ SiO _2/2 ), (A8SiO _3/2 ), (HFPO3SiO _3/2 ) And (O _1/2 H) units, (A8SiO _3/2 ) and (O _1/2 H) units organopolysiloxane resins, (A3MeSiO _2/2 ), (A8SiO _{3 / 2} ) and (O _1/2 H) unit organopolysiloxane resin, (A8SiO _3/2 ), (A3SiO _3/2 ) and (O _1/2 H) unit organopolysiloxane resin, (A8SiO _{3) / 2} ), (A1SiO _3/2 ) and (O _1/2 H) units, (A8SiO _3/2 ), (A1SiO _3/2 ), (A3SiO _3/2 ) and (O ₁ Oh consisting _{/ 2} H) unit Ganoderma polysiloxane _{resin, (A8SiO 3/2), (MeSiO} 3/2) and (O _1/2 H) composed of units organopolysiloxane _{resin, (A8SiO 3/2), (HFPO3SiO} 3/2) and (O Organopolysiloxane resin composed of _1/2 H) units, (R ^SE Me ₂ SiO _1/2 ), (Me ₂ SiO _2/2 ), (R ^SE SiO _3/2 ), (A8SiO _3/2 ), ( Organopolysiloxane resin comprising HFPO3SiO _3/2 ) and (O _1/2 H) units [where Me is a methyl group, A8 is an 8- (meth) acryloxyoctyl group, and A1 is a (meth) acryloxymethyl group , A3 is 3- (meth) acryloxy propyl group, HFPO3 is _{C 3 F 7 OC (CF 3} ) FCF 2 OC (CF 3) FCH 2 OC 3 H 6 - an organic group represented, R ^SE is 2- Silylethyl group] and the like are exemplified. The present invention is not limited to.
In the present invention, 2-silylethyl group R ^SE _{is, -CH 2 CH 2 Si (Y} 3-p) Z p ( where, Y is an alkyl group such as a methyl group, an ethyl group, Z is methoxy, ethoxy Silylethyl containing 2 or 3 hydrolyzable groups such as trialkoxysilylethyl group and alkyldialkoxysilylethyl group represented by the following formula: Refers to the group.

  The weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) of the silicone resin represented by the siloxane unit formula (1) of the present invention as a developing solvent is 2,000 to 10,000. It is preferable that it is 2,500 to 8,000. If it is less than 2,000, condensation is not sufficient, storage stability is poor, unreacted siloxane units may remain, and repellency may occur on the surface of the film. If it is greater than 10,000, the viscosity becomes high and handling may be difficult.

  Moreover, it is preferable that silanol group content of the obtained silicone resin 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 silicone resin preferably has a volatile content (105 ° C./3 hours) of an organic solvent or the like of less than 1% by mass.
Further, when the silicone resin is liquid at room temperature (25 ° C.), the viscosity measured by a rotational viscometer is 1,000 to 10,000, particularly 1,500 to 5,000 mPa · s. preferable.

  The curable resin composition containing the organopolysiloxane resin (silicone resin) represented by the siloxane unit formula (1) according to the present invention may include a polyfunctional (meth) acrylate as a reactive diluent, if necessary. It is preferable to include. When polyfunctional (meth) acrylate is not included, the organopolysiloxane resin becomes solid (crystallized) or increases in viscosity, which makes it difficult to manufacture stably and makes it very difficult to apply to substrates. There is a risk.

The polyfunctional (meth) acrylate forms a matrix of the 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, dicyclopentadienyl diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, 3- (meth) acryloyloxyglycerin mono (meth) acrylate, urethane acrylate, epoxy acrylate, ester acrylate, etc. Including but not necessarily limited thereto.
These compounds may use only 1 type and may use 2 or more types together.

  The blending amount of the polyfunctional (meth) acrylate is preferably 0 to 500 parts by mass, particularly preferably 0 to 400 parts by mass with respect to 100 parts by mass of the silicone resin. If the amount of polyfunctional (meth) acrylate is too large, sufficient wear resistance may not be obtained. In addition, when mix | blending polyfunctional (meth) acrylate, it is preferable that it is 10 mass parts or more from the point which exhibits the effect effectively.

  The curable resin composition containing the organopolysiloxane resin (silicone resin) represented by the siloxane unit formula (1) and, if necessary, a polyfunctional (meth) acrylate is a photocuring catalyst, a radical polymerization catalyst, a thermal condensation. By mixing any one or more curing catalysts of the catalyst, a curable resin composition curable by light and / or heat can be obtained, which is cured by high energy rays such as ultraviolet rays or heat. It is.

  Here, a radical initiator and / or a thermal condensation catalyst can be used as the curing catalyst. The radical 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 condensation catalyst used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, sodium formate, n-hexylamine, tributylamine, diazabicycloundecene and the like. Basic compounds, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, cobalt octylate, cobalt acetylacetonate, zinc octylate, zinc Metal-containing compounds such as acetylacetonate, iron acetylacetonate, tin acetylacetonate, dibutyltin octylate, dibutyltin laurate, p-toluenesulfonic acid, trimethyl Acidic compounds such as Le acetate.

  The blending amount of the curing catalyst can be 0.1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the silicone resin and the polyfunctional (meth) acrylate. 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 may be deteriorated, and if it is more than 15 parts by mass, the surface hardness may be lowered.

  The curable resin composition containing the organopolysiloxane resin (silicone resin) represented by the above siloxane unit formula (1) of the present invention may further comprise metal oxide fine particles, silane coupling agent, non-polymerizable, if necessary. Diluting solvent, polymerization inhibitor, antioxidant, ultraviolet absorber, light stabilizer, antifoaming agent, leveling agent and the like.

  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 fine 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, when mix | blending metal oxide microparticles | fine-particles, such as a silica microparticle, the compounding quantity has preferable 5-100 mass parts with respect to 100 mass parts of total amounts of a silicone resin and polyfunctional (meth) acrylate.

  The curable resin composition curable with light and / or heat of the present invention is a molding material such as various functional films represented by a transparent conductive film for touch panels, more specifically, high transparency, high dimensional stability, In addition to being a molding material that provides a film with a good balance between crack resistance and wear resistance, articles that require an antifouling layer on the surface, especially read-only optical disks, optical recording disks, and magneto-optical recording disks More specifically, the surface of an optical information medium such as a recording or reproducing beam incident surface, an optical lens, an optical filter, an antireflection film, and various display elements such as a liquid crystal display, a CRT display, a plasma display, an EL display, etc. By applying to the surface and making it a hardened film, antifouling effect against contaminants such as scratch resistance, crack resistance and fingerprint stains on these surfaces It is possible to impart wiping of marker ink, an article having the cured film may be assumed to be excellent in scratch resistance and abrasion resistance is excellent in antifouling property and lubricating property.

As a method for obtaining a molded product by the resin composition of the present invention, for example, it is injected into a mold having an arbitrary cavity shape and made of a transparent material such as quartz glass, and cured by actinic ray irradiation described later. The resin composition of the present invention using a doctor blade or a roll-shaped coater on a moving steel belt in the case of not using a mold, or a method for producing a molded product of a desired shape by demolding from a mold The method etc. which manufacture a sheet-like molded article by apply | coating a thing and making it harden | cure by active ray irradiation can be illustrated.
The thickness of the formed product is preferably 10 μm to 10 mm, particularly 50 μm to 1 mm.

As a method of forming a film with the resin composition of the present invention, the film can be prepared by a spin coat 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 wear resistance and the like may be saturated, and the cost for imparting desired characteristics may become unnecessarily high.

As a light source for photocuring the resin composition of the present invention, usually a light source containing light having a wavelength in the range of 200 to 450 nm, such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, etc. Can be used. Although the amount of irradiation is not particularly limited, it is preferably 10 to 5,000 mJ / cm ² , particularly preferably ²⁰ to 2,000 mJ / cm ² . The curing time is usually 0.5 seconds to 2 minutes, preferably 1 second to 1 minute.

  For the heat curing of the resin composition of the present invention, 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 of ° C.

  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, Me represents a methyl group. In addition, the volatile content indicates a value measured by mass reduction when held at 105 ° C. for 3 hours, and the refractive index indicates a value at 25 ° C. measured by a refractometer (ATAGO CO., LTD, RX-7000α). The amount of SiOH groups indicates a value converted by the amount of methane generated when methylmagnesium bromide is allowed to act, and the weight average molecular weight indicates a polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

Various properties were evaluated by the following methods.
[Molded product characteristics]
Glass transition temperature dynamic thermomechanical analysis, heating rate 5 ° C / min, chuck distance 10mm
Linear expansion coefficient thermomechanical analysis, heating rate 5 ° C / min, compressive load 0.1N
Total light transmittance JIS K 7361-1 conformity, sample thickness 0.2mm
Birefringence spectroscopic ellipsometry, sample thickness 0.2mm

[Hardened film properties]
A line was drawn with a commercially available oil-based magic ink on the magic ink-resistant cured film, and the wiping property when wiping with a waste cloth was visually observed.
○: Wiping property △: Wiping property is slightly present ×: Wiping property is not present
The antifouling water contact angle and trioleic acid contact angle were measured using a contact angle meter (CA-X150, manufactured by Kyowa Interface Science) (the larger the contact angle, the better the antifouling property).
Abrasion resistance and abrasion resistance In accordance with ASTM D 1044, the abrasion test (500 gf load 100 revolutions) of the hardened film (sample thickness 5 μm) is performed using a Taber abrasion tester (with wear wheel CS-10F). The turbidity of the cured film before and after the test was measured using a turbidimeter (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 and abrasion resistance are good.)
The degree of warpage (curl) of the entire film due to shrinkage due to curing shrinkage The film edge when a cured film is formed with a thickness of 5 μm on a 10 cm × 10 cm PET (polyethylene terephthalate) film and fixed to the horizontal plane at the center point of the film The distance from the horizontal plane of the part was evaluated (the larger the value, the greater the shrinkage).

[Synthesis Example 1]
As starting materials, 318.5 parts by mass (1.00 mol) of methacryloxyoctyltrimethoxysilane and 914.0 parts by mass of isopropyl alcohol were mixed in a reactor. When uniform, 20% by mass of tetramethylammonium hydroxide was mixed. 15.3 parts by mass of an aqueous solution and 95.5 parts by mass of water (water total 6.0 mol) were added, and the mixture was 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 had a volatile content of 0.5% by mass, a refractive index of 1.4765, a SiOH group content of 0.8% by mass, and a weight average molecular weight of 8,800. This reaction product undergoes hydrolysis and condensation as ideal from the results of infrared absorption analysis and nuclear magnetic resonance analysis, and has a siloxane unit formula [MA8SiO _3/2 ] _1.0 [OH] _0.12 [MA8: methacryloxyoctyl]. It was confirmed that it was a reactive group-containing organopolysiloxane resin.

[Synthesis Example 2]
As starting materials, 254.8 parts by mass (0.80 mol) of methacryloxyoctyltrimethoxysilane, 46.8 parts by mass (0.20 mol) of 3-acryloxypropyltrimethoxysilane, and 569.7 parts by mass of isopropyl alcohol When blended in the reactor and uniform, 15.3 parts by mass of 20% by mass tetramethylammonium hydroxide aqueous solution and 95.5 parts by mass of water (total 6.0 mol of water) were added and stirred at 25 ° C. for 12 hours. did. 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 0.8% by mass, a refractive index of 1.4760, a SiOH group content of 0.4% by mass, and a weight average molecular weight of 7,200. This reaction product undergoes hydrolysis and condensation as ideal from the results of infrared absorption light analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [MA8SiO _3/2 ] _0.8 [AC3SiO _3/2 ] _0.2 [OH] _0.05 [MA8 : Methacryloxyoctyl, AC3: 3-acryloxypropyl] was confirmed to be a photoreactive group-containing organopolysiloxane resin.

[Synthesis Example 3]
As starting materials, 286.7 parts by mass (0.90 mol) of methacryloxyoctyltrimethoxysilane, 13.6 parts by mass (0.10 mol) of methyltrimethoxysilane, and 503.1 parts by mass of isopropyl alcohol were blended in a reactor. When it became uniform, 15.3 parts by mass of a 20% by mass tetramethylammonium hydroxide aqueous solution and 95.5 parts by mass of water (6.0 mol in total) were 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 had a volatile content of 0.6% by mass, a refractive index of 1.74749, a SiOH group content of 0.8% by mass, and a weight average molecular weight of 5,700. This reaction product undergoes hydrolysis and condensation as ideal based on the results of infrared absorption optical analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [MA8SiO _3/2 ] _0.9 [MeSiO _3/2 ] _0.1 [OH] _0.11 [MA8 : Methacryloxyoctyl] was confirmed to be a photoreactive group-containing organopolysiloxane resin.

[Synthesis Example 4]
As starting materials, 308.9 parts by mass (0.97 mol) of methacryloxyoctyltrimethoxysilane, 19.3 parts by mass (0.03 mol) of HFPO ₃ Si (OMe) ₃ [HFPO ₃ : C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —] and isopropyl alcohol were blended in a 608.5 part by mass reactor, and when uniform, 15.3 parts by mass of a 20% by mass tetramethylammonium hydroxide aqueous solution, 95.5 parts by mass of water (water total 6.0 mol) 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 had a volatile content of 0.6% by mass, a refractive index of 1.4792, a SiOH group content of 0.8% by mass, and a weight average molecular weight of 7,600. This reaction product undergoes hydrolytic condensation as ideal based on the results of infrared absorption light analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [MA8SiO _3/2 ] _0.97 [HFPO3SiO _3/2 ] _0.03 [OH] _0.12 [MA8 : Methacryloxyoctyl, HFPO3: a photoreactive group-containing organopolysiloxane resin having C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —].

[Synthesis Example 5]
As starting materials, 305.8 parts by mass (0.96 mol) of methacryloxyoctyltrimethoxysilane, 19.3 parts by mass (0.03 mol) of HFPO ₃ Si (OMe) ₃ [HFPO ₃ : C ₃ F ₇ OC (CF ₃ ) FCF _{2 OC (CF 3) FCH 2} OC 3 H 6 -], 1,19- bis (trimethoxysilyl ethyl) - 0.9 parts by weight per methyl deca siloxane (0.01 mol), 612.7 parts by mass of isopropyl alcohol When mixed in a partial reactor and uniform, 155.3 parts by weight of a 20% by weight tetramethylammonium hydroxide aqueous solution and 95.5 parts by weight of water (total of 6.0 mols of water) are added, and the mixture is heated 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 0.2% by mass, a refractive index of 1.4733, a SiOH group content of 0.3% by mass, and a weight average molecular weight of 5,700. This reaction product undergoes hydrolysis and condensation as ideal based on the results of infrared absorption optical analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [R ^SE Me ₂ SiO _1/2 ] _0.002 [Me ₂ SiO _2/2 ] _0.006 [R ^SE SiO _3/2 ] _0.002 [MA8SiO _3/2 ] _0.96 [HFPO3SiO _3/2 ] _0.03 [OH] _0.06 [R ^SE : 2-silylethyl, MA8: methacryloxyoctyl, HFPO3: C ₃ F ₇ OC (CF ₃ ) It was confirmed that the photoreactive group-containing organopolysiloxane resin had FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —].

[Comparative Synthesis Example 1]
As starting materials, 234.0 parts by mass (1.00 mol) of 3-acryloxypropyltrimethoxysilane and 539.7 parts by mass of isopropyl alcohol were blended in a reactor. Hydroxide aqueous solution 15.3 mass parts and water 95.5 mass parts (water total 6.0 mol) were added, and it stirred at 25 degreeC 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 had a volatile content of 0.3% by mass, a refractive index of 1.4805, a SiOH group content of 0.4% by mass, and a weight average molecular weight of 3,000. This reaction product undergoes hydrolysis and condensation as ideal based on the results of infrared absorption light analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [AC3SiO _3/2 ] _1.0 [OH] _0.03 [AC3: 3-acryloxypropyl] It was confirmed that the photoreactive group-containing organopolysiloxane resin had

[Comparative Synthesis Example 2]
As starting materials, 226.8 parts by mass (0.97 mol) of 3-acryloxypropyltrimethoxysilane, 19.3 parts by mass (0.03 mol) of HFPO ₃ Si (OMe) ₃ [HFPO ₃ : C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —] and isopropyl alcohol were blended in a 608.5 parts by mass reactor, and when uniform, 15.3% by mass of 20 mass% tetramethylammonium hydroxide aqueous solution. Part, 95.5 parts by weight of water (water total 6.0 mol) 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 had a volatile content of 0.6% by mass, a refractive index of 1.4717, a SiOH group amount of 0.56% by mass, and a weight average molecular weight of 2,200. This reaction product undergoes hydrolysis and condensation as ideal based on the results of infrared absorption optical analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [AC3SiO _3/2 ] _0.97 [HFPO3SiO _3/2 ] _0.03 [OH] _0.04 [AC3 : _{3-acryloxypropyl, HFPO3: C 3 F 7 OC} (CF 3) FCF 2 OC (CF 3) FCH 2 OC 3 H 6 - was confirmed to be] photoreactive group-containing organopolysiloxane resin having a .

[Comparative Synthesis Example 3]
As starting materials, 224.6 parts by mass (0.96 mol) of 3-acryloxypropyltrimethoxysilane, 19.3 parts by mass (0.03 mol) of HFPO ₃ Si (OMe) ₃ [HFPO ₃ : C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —], 0.9 parts by mass (0.01 mol) of 1,19-bis (trimethoxysilylethyl) -permethyldecasiloxane, and 612. In a 7 mass part reactor, when it became uniform, 15.3 mass parts of 20 mass% tetramethylammonium hydroxide aqueous solution and 95.5 mass parts of water (water total 6.0 mol) were added, and 25 degreeC was added. Stir 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 had a volatile content of 0.5% by mass, a refractive index of 1.4829, a SiOH group content of 0.6% by mass, and a weight average molecular weight of 3,000. This reaction product undergoes hydrolysis and condensation as ideal based on the results of infrared absorption optical analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [R ^SE Me ₂ SiO _1/2 ] _0.002 [Me ₂ SiO _2/2 ] _0.006 [R ^SE SiO _3/2 ] _0.002 [AC3SiO _3/2 ] _0.96 [HFPO3SiO _3/2 ] _0.03 [OH] _0.043 [R ^SE : 2-silylethyl, AC3: 3-acryloxypropyl, HFPO3: C ₃ F ₇ OC It was confirmed that the photoreactive group-containing organopolysiloxane resin had (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —].

[Example 1]
Organopolysiloxane resin obtained in Synthesis Example 1: 25 parts by mass, trimethylolpropane triacrylate: 10 parts by mass, dicyclopentadienyl diacrylate (Kyoeisha Chemical Co., Ltd. light acrylate DCP-A): 60 parts by mass, Urethane acrylate oligomer (UF-8001 manufactured by Kyoeisha Chemical Co., Ltd.): 5 parts by mass, Darocur 1173 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.): 2.5 parts by mass as a photopolymerization initiator, and a transparent resin composition I got a thing.
Next, the film was cast to a thickness of 0.2 mm using a roll coater, and irradiated with light with an 80 W high-pressure mercury lamp for 2 seconds (integrated irradiation amount: 200 mJ / cm ² ) to cure to a predetermined thickness. A molded body was obtained.

[Examples 2 and 3 and Comparative Example 1]
A resin molded body was obtained in the same manner as in Example 1 except that the composition was changed to the ratio shown in Table 1. Table 2 summarizes the physical property values of the obtained molded body.

The abbreviations in the table are as follows.
Resin A: Resin manufactured in Synthesis Example 1 Resin B: Resin manufactured in Synthesis Example 2 Resin C: Resin manufactured in Synthesis Example 3 Resin F: Resin manufactured in Comparative Synthesis Example 1 TMPTA: Trimethylolpropane triacrylate DCP- A: Dicyclopentadienyl diacrylate UAOL: Urethane acrylate oligomer D1173: Photopolymerization initiator: Darocur 1173

[Example 4]
Organopolysiloxane resin obtained in Synthesis Example 1: 60 parts by mass, hexanediol diacrylate: 40 parts by mass, Darocur 1173 (trade name, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator: 5 parts by mass are mixed and transparent A resin composition was obtained.
Next, using a bar coater (No. 5), it was applied to a polycarbonate plate so as to have a thickness of 5 μm, and was irradiated with light with an 80 W high-pressure mercury lamp for 2 seconds (accumulated dose 200 mJ / cm ² ) to be cured.

[Examples 5 to 8 and Comparative Examples 2 to 4]
A cured film was obtained in the same manner as in Example 4 except that the composition was changed to the ratio shown in Table 3. Table 4 summarizes the physical property values of the obtained cured film.

The abbreviations in the table are as follows.
Resin A: Resin manufactured in Synthesis Example 1 Resin B: Resin manufactured in Synthesis Example 2 Resin C: Resin manufactured in Synthesis Example 3 Resin D: Resin manufactured in Synthesis Example 4 Resin E: Resin manufactured in Synthesis Example 5 Resin F: Resin manufactured in Comparative Synthesis Example 1 Resin G: Resin manufactured in Comparative Synthesis Example 2 Resin H: Resin manufactured in Comparative Synthesis Example 3 HDODA: Hexanediol diacrylate D1173: Photopolymerization initiator: Darocur 1173

  The above examples and comparative examples show that the resin composition of the present invention is effective as a functional film material and an antifouling scratch-resistant coating material while achieving a high balance of hardness and flexibility. It is.

Claims (12)

The following siloxane unit formula (1)

[Wherein, X is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{1 to} R ⁶ are independently monovalent hydrocarbons having 1 to 10 carbon atoms which may have a substituent. The above substituents are phenyl, fluorine, chlorine, bromine, (meth) acryloxy, epoxy structure-containing, mercapto, isocyanate, amino functional, perfluoroalkyl, poly (hexa). Fluoropropylene oxide) is a monovalent organic group selected from a structure-containing group and a silyl group. However, in any one of R ^{1 to} R ⁶ , the formula (2)
^{_{CH 2 = C (R 7)}} COO (CH 2) n - (2)
(In the formula, R ⁷ is a hydrogen atom or a methyl group, and n is an integer of 4 or more.)
The siloxane units substituted by the organic group represented by the formula (2) with respect to the total siloxane units are 20 to 100 mol%, and a is an average of 0 ≦ a <0. .4, b is on average 0 ≦ b <0.5, c is on average 0 <c ≦ 1, d is on average 0 ≦ d <0.4, and e is on average 0 ≦ e <0 .2 and a + b + c + d = 1. ]
The curable resin composition characterized by including the silicone resin represented by these , and a polyfunctional (meth) acryl compound .   2. The resin composition according to claim 1, wherein n of the organic group represented by the formula (2) is 8. The resin composition according to claim 1 or 2, wherein the silicone resin has a weight average molecular weight of 2,000 to 10,000. The resin composition according to any one of claims 1 to 3, wherein the silicone resin has a silanol group content of 2 mass% or less. The resin composition according to any one of claims 1 to 4, wherein a volatile component contained in the silicone resin is less than 1% by mass.   The resin composition according to any one of claims 1 to 5, which is solvent-free and is liquid at room temperature. The silicone resin contains 0.1 to 20 mol% of a siloxane unit substituted with a perfluoroalkyl group or a poly (hexafluoropropylene oxide) structure-containing group with respect to the total siloxane units. Item 1. The resin composition according to item 1. Further, the resin composition of any one of claims 1-7, characterized in that it comprises a metal oxide fine particles. The resin composition according to any one of claims 1 to 8 , further comprising at least one of a photocuring catalyst, a radical polymerization catalyst, and a thermal condensation catalyst. A molded product obtained by curing the resin composition according to any one of claims 1 to 9 . Coating of the resin composition of any one of claims 1-9. An article formed with a cured film of the coating agent according to claim 11 .