JP2018178003A - Fluorine-containing epoxy-modified silsesquioxane and curable composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel fluorine-containing epoxy-modified silsesquioxane capable of forming a cured product excellent in scratch resistance.SOLUTION: The fluorine-containing epoxy-modified silsesquioxane of the present invention has a siloxane constituent unit (T-1) represented by formula (T-1): [RSiO] [where Rrepresents a group containing an epoxy group] and a siloxane constituent unit (T-2) represented by formula (T-2): [RSiO] [where Rrepresents a group obtained by substituting two or more hydrogen atoms of a C2-16 alkyl group with fluorine atoms].SELECTED DRAWING: None

Description

  The present invention relates to novel fluorine-containing epoxy-modified silsesquioxanes and curable compositions using the fluorine-containing epoxy-modified silsesquioxanes.

  Hard coat films used by being attached to the surface of various displays are required to have surface hardness and scratch resistance. Patent Document 1 describes that a hard coat film provided with a cured film of a hard coat agent containing epoxy-modified silsesquioxane has the above-mentioned properties. However, further improvement of scratch resistance is required.

JP, 2015-193747, A

Accordingly, an object of the present invention is to provide a novel fluorine-containing epoxy-modified silsesquioxane capable of forming a cured product having excellent scratch resistance.
Another object of the present invention is to provide a curable composition capable of forming a cured product having the above-mentioned fluorine-containing epoxy-modified silsesquioxane and having excellent scratch resistance.
Furthermore, another object of the present invention is to provide a hard coat film provided with a cured film of the curable composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that silsesquioxane having an epoxy group and a fluorine-substituted alkyl group can form a cured product having excellent scratch resistance by cationic polymerization. Found out. The present invention has been completed based on these findings.

That is, the present invention provides the following formula (T-1)
[R ¹ SiO _3/2 ] (T-1)
[Wherein, R ¹ represents a group containing an epoxy group]
And a siloxane structural unit (T-1) represented by
Following formula (T-2)
[R ² SiO _3/2 ] (T-2)
[Wherein, R ² represents a group in which two or more hydrogen atoms of an alkyl group having 2 to 16 carbon atoms are substituted with a fluorine atom]
And a fluorine-containing epoxy-modified silsesquioxane having a siloxane structural unit (T-2) represented by

  In the present invention, the total of the siloxane structural unit (T-1) and the siloxane structural unit (T-2) in all the siloxane structural units (100 mol%) constituting the fluorine-containing epoxy-modified silsesquioxane A fluorine having a ratio of 80 mol% or more and a molar ratio of the siloxane structural unit (T-1) to the siloxane structural unit (T-2) (former / latter) of 90/10 to 10/90 An epoxy-modified silsesquioxane is provided.

  The present invention also provides the fluorine-containing epoxy-modified silsesquioxane as described above, which has a polystyrene-equivalent number average molecular weight (Mn) of 500 to 4000 as measured by gel permeation chromatography.

［式中、Ｒ^1a、Ｒ^1b、Ｒ^1c、及びＲ^1dは、同一又は異なって、直鎖又は分岐鎖状のアルキレン基を示す］ The present invention is also characterized in that the R ¹ is one or more groups selected from the group consisting of groups represented by the following formulas (1a), (1b), (1c), and (1d) And a fluorine-containing epoxy-modified silsesquioxane.

[Wherein, R ^1a , R ^1b , R ^1c and R ^1d are the same or different and represent a linear or branched alkylene group]

  The present invention also provides a curable composition comprising the above-mentioned fluorine-containing epoxy-modified silsesquioxane.

  The present invention also provides the curable composition as described above, which is a hard coating agent.

  The present invention also provides a hard coat film provided with a cured film of the above-mentioned curable composition.

  The fluorine-containing epoxy-modified silsesquioxane of the present invention can improve the scratch resistance of the resulting cured product by adding it to the curable composition. In addition, the fluorine-containing epoxy-modified silsesquioxane of the present invention does not impair the transparency of the resulting cured product even when added to the curable composition. Therefore, the fluorine-containing epoxy-modified silsesquioxane of the present invention can be suitably used as a scratch resistance imparting agent and the like.

FIG. 2 is a diagram showing a ²⁹ Si-NMR spectrum of the fluorine-containing epoxy-modified silsesquioxane obtained in Example 1. FIG. 2 is a diagram showing ¹ H-NMR spectrum of the fluorine-containing epoxy-modified silsesquioxane obtained in Example 1. FIG. 2 is a diagram showing a ²⁹ Si-NMR spectrum of a fluorine-containing epoxy-modified silsesquioxane obtained in Example 2. FIG. 2 is a diagram showing ¹ H-NMR spectrum of the fluorine-containing epoxy-modified silsesquioxane obtained in Example 2. It is a figure which shows the abrasion resistance of the hard coat film obtained by Example 3, 4 and the comparative example 1. FIG. It is a figure which shows the abrasion resistance of the hard coat film obtained by Example 5 and Comparative Example 1.

[Fluorine-containing epoxy-modified silsesquioxane]
The fluorine-containing epoxy-modified silsesquioxane of the present invention has the following formula (T-1)
[R ¹ SiO _3/2 ] (T-1)
[Wherein, R ¹ represents a group containing an epoxy group]
And a siloxane structural unit (T-1) represented by
Following formula (T-2)
[R ² SiO _3/2 ] (T-2)
[Wherein, R ² represents a group in which two or more hydrogen atoms of an alkyl group having 2 to 16 carbon atoms are substituted with a fluorine atom]
And a siloxane structural unit (T-2) represented by

  The siloxane structural unit (T-1) and the siloxane structural unit (T-2) are T units (units in which three oxygen atoms are bonded to one silicon atom), and in detail, the formula (t3) described later It is T3 body represented by

R ¹ in the formula (T-1) represents a group (monovalent group) containing an epoxy group. That is, the fluorine-containing epoxy-modified silsesquioxane of the present invention is a cationic curable compound having at least an epoxy group in the molecule. Examples of the group containing an epoxy group include known or commonly used groups having an oxirane ring, which are not particularly limited, but are represented by the following formula (1a) from the viewpoint of the curing property and heat resistance of the curable composition Groups, groups represented by the following formula (1b), groups represented by the following formula (1c), and groups represented by the following formula (1d) are preferable, and more preferably represented by the following formula (1a) And a group represented by the following formula (1c), more preferably a group represented by the following formula (1a).

In the above formulae, R ^1a , R ^1b , R ^1c and R ^1d are the same or different and each represents a linear or branched alkylene group. As a linear or branched alkylene group, for example, methylene group, methyl methylene group, dimethyl methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, decamethylene group, etc. A C1-C10 linear or branched alkylene group is mentioned. In the present invention, among them, from the viewpoint of curability, a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 to 4 carbon atoms are preferable, and ethylene and trimethylene groups are more preferable, Propylene group is more preferable such as ethylene group and trimethylene group.

Particularly, R ¹ in the formula (T-1) is a group represented by the above formula (1a), and a group in which R ^1a is an ethylene group or a trimethylene group [in particular, 2- (3,4- Epoxycyclohexyl) ethyl group] is preferable.

R ² in the formula (T-2) is at least two hydrogen atoms of an alkyl group (preferably linear alkyl group) having 2 to 16 (preferably 3 to 10, particularly preferably 3 to 6) carbon atoms Is a group substituted with a fluorine atom (fluorinated alkyl group). Among them, a group represented by the following formula (r2) is preferable. In the following formulas, n is an integer of 1 or more, preferably 1 to 8, particularly preferably 1 to 5, and most preferably 1 to 3. m is an integer of 0 or more, preferably 0 to 8, particularly preferably 0 to 5, and most preferably 0 to 4. The left end of the following formula is bonded to the silicon atom in formula (T-2).
_{- (CH 2) n - (} CF 2) m -CF 3 (r2)

  The fluorine-containing epoxy-modified silsesquioxane of the present invention only needs to have a siloxane structural unit (T-1) and a siloxane structural unit (T-2) as T units, and each siloxane structural unit is one kind. Or a combination of two or more.

  The proportion of the sum of the siloxane structural unit (T-1) and the siloxane structural unit (T-2) in all the siloxane structural units (100 mol%) constituting the fluorine-containing epoxy-modified silsesquioxane of the present invention is For example, it is 80 mol% or more, preferably 85 mol% or more, and particularly preferably 90 mol% or more. The upper limit is 100 mol%. The fluorine-containing epoxy-modified silsesquioxane containing the siloxane structural units (T-1) and (T-2) in the above-mentioned range tends to be particularly excellent in the effect of imparting scratch resistance to a cured product.

The fluorine-containing epoxy-modified silsesquioxane of the present invention may have other siloxane structural units in addition to the siloxane structural unit (T-1) and the siloxane structural unit (T-2) as T units. The T3 body may have a siloxane structural unit (T-3) represented by the following formula (T-3). Furthermore, it may have a siloxane structural unit represented by the following formulas (T-1 ′) and (T-2 ′) as a T2 body.
[R ³ SiO _3/2 ] (T-3)
[R ¹ SiO _2/2 (OR ⁴ )] (T-1 ')
[R ² SiO _2/2 (OR ⁴ )] (T-2 ')
(Wherein, R ¹ and R ² are the same as above. R ³ represents a hydrogen atom or a hydrocarbon group which may have a substituent (excluding a halogen atom and an epoxy group). R ⁴ is the same. Or different, it represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

More specifically, the T3 body is represented by the following formula (t3). Further, the T2 body is more specifically represented by the following formula (t2). The three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (t3) are each bonded to another silicon atom (a silicon atom not shown in the formula (t3)). On the other hand, two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (t2) are each bonded to another silicon atom (a silicon atom not shown in the formula (t2)) doing. In the following formulae, R represents the above R ¹ , R ² or R ³ . R ⁴ is the same as above.

The hydrocarbon group in the above R ^3, an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon groups, and these groups bound to each.

  The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group and a t-butyl group. Alkyl group having 1 to 10 (preferably 1 to 5, particularly preferably 1 to 3) carbon atoms such as pentyl group and isopentyl group; 2 to 10 carbon atoms such as vinyl, allyl and 1-butenyl group Preferably, an alkenyl group of 2 to 5 and particularly preferably 2 to 3); an alkynyl group having 2 to 10 carbon atoms (preferably 2 to 5 and particularly preferably 2 to 3) such as ethynyl group and propynyl group etc. Can.

  The alicyclic hydrocarbon group is preferably a 3- to 10-membered alicyclic hydrocarbon group, and for example, a 3- to 10-membered (preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc.) 5-8 membered cycloalkyl group; 3-10 membered (preferably 5-8 membered) cycloalkenyl group such as cyclopentenyl group, cyclohexenyl group and the like can be mentioned.

  As an aromatic hydrocarbon group, a C6-C14 (especially C6-C10) aromatic hydrocarbon group is preferable, For example, a phenyl group, a naphthyl group, etc. can be mentioned.

As the substituent which the above-mentioned hydrocarbon group may have, for example, oxo group, hydroxyl group, substituted oxy group (for example, C _1-3 alkoxy group, C _6-10 aryloxy group, C _7-10 aralkyl) Oxy group, acyloxy group etc.), carboxyl group, substituted oxycarbonyl group (eg, C _1-3 alkoxycarbonyl group, C _6-10 aryloxycarbonyl group, C _7-10 aralkyloxycarbonyl group etc.), substituted or unsubstituted A carbamoyl group, a cyano group, a nitro group, an amino group, a mercapto group, a (meth) acryl group etc. are mentioned.

The alkyl group having 1 to 4 carbon atoms in the R ^4, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, include straight chain or branched chain alkyl groups such as isobutyl.

  The molar ratio [T3 body / T2 body] of T3 body to T2 body contained in all the siloxane structural units constituting the fluorine-containing epoxy-modified silsesquioxane of the present invention is, for example, 5 to 40, and the scratch resistance is Preferably, it is 10 to 30, particularly preferably 15 to 25, and most preferably 20 to 25 in that the effect of improving

The molar ratio [T3 body / T2 body] of the T3 body and the T2 body can be determined, for example, by ²⁹ Si-NMR spectrum measurement. ^{In the 29} Si-NMR spectrum, silicon atoms in the T3 body and silicon atoms in the T2 body show signals (peaks) at different positions (chemical shifts), so by calculating the integral ratio of these respective peaks, [T3 body / T2 body] is obtained. In addition, the signal of the silicon atom in T3 body appears in -64 to -70 ppm, and the signal of the silicon atom in T2 body appears in -54 to -60 ppm.

^{The 29} Si-NMR spectrum can be measured, for example, by the following apparatus and conditions.
Measuring device: Brand name "JNM-ECA 500 NMR" (manufactured by Nippon Denshi Co., Ltd.)
Solvent: Heavy chloroform Accumulated number of times: 1800 times Measurement temperature: 25 ° C

The fluorine-containing epoxy-modified silsesquioxane of the present invention is not limited to the T unit described above, and M unit [R ₃ SiO _1/2 ], D unit [R ₂ SiO _2/2 ], Q unit [SiO _4/2 ] It may have one or two or more. In addition, said R shows said R < ¹ >, R < ² > or R < ³ >.

  The fluorine atom content of the fluorine-containing epoxy-modified silsesquioxane of the present invention is, for example, 0.1 mol or more and less than 10 mol of fluorine atoms per 1 mol of silicon atoms contained in the fluorine-containing epoxy-modified silsesquioxane The upper limit is preferably 5 moles, more preferably 2.5 moles, particularly preferably 2.0 moles, most preferably 1.8 moles, especially preferably 1.5 moles. When the fluorine-containing epoxy-modified silsesquioxane of the present invention contains a fluorine atom in the above range, it has compatibility with other cation-curable compounds such as epoxy-modified silsesquioxane, and other cation-curable compounds By adding it, abrasion resistance of the hardened | cured material obtained can be improved. On the other hand, when the fluorine atom content is excessive, the compatibility with other cationically curable compounds such as epoxy-modified silsesquioxane tends to be reduced and mixing tends to be difficult.

  The epoxy equivalent (g / eq) of the fluorine-containing epoxy-modified silsesquioxane of the present invention is, for example, 150 to 500, preferably 170 to 400, and particularly preferably 190 to 350. It is especially excellent in the polymerizability with other cation hardenability compounds as the above-mentioned epoxy equivalent is in the above-mentioned range, and the abrasion resistance of the hardened material obtained can be improved remarkably. Moreover, there exists a tendency to be excellent in the crack resistance of hardened | cured material, and adhesiveness with respect to a to-be-adhered body. Furthermore, the heat resistance tends to be excellent. The epoxy equivalent is measured in accordance with JIS K 7236: 2001.

  The number average molecular weight (Mn) in terms of standard polystyrene equivalent by gel permeation chromatography of the fluorine-containing epoxy-modified silsesquioxane of the present invention is not particularly limited, but for example 500 to 4000, preferably 1000 to 2500, particularly preferably 1200 ~ 1800, most preferably 1300-1700. When the number average molecular weight of the fluorine-containing epoxy-modified silsesquioxane is 500 or more, the curable composition containing the same has good film forming properties, and when applied to a substrate or the like, repelling hardly occurs, It is hard to produce a dent and a dent on the coating film surface. The cured product of the curable composition is particularly excellent in heat resistance and scratch resistance. On the other hand, when the number average molecular weight of the fluorine-containing epoxy-modified silsesquioxane is 4000 or less, the compatibility with other components contained in the curable composition is excellent.

  Although the molecular weight dispersion degree (Mw / Mn) of standard polystyrene conversion by gel permeation chromatography of fluorine-containing epoxy-modified silsesquioxane of the present invention is not particularly limited, it is 3.0 or less (for example, 1.0 to 3. 0) is preferable, More preferably, it is 1.1-2.0, More preferably, it is 1.1-1.5. When the molecular weight dispersion of the fluorine-containing epoxy-modified silsesquioxane is 3.0 or less, the cured product of the curable composition containing the same is particularly excellent in the scratch resistance. On the other hand, when the molecular weight dispersion degree of the fluorine-containing epoxy-modified silsesquioxane is 1.1 or more, it becomes easily liquid, and the handleability is good.

In addition, the number average molecular weight of the fluorine-containing epoxy modified silsesquioxane of this invention and molecular weight dispersion degree can be measured by the following apparatus and conditions.
Measuring device: Brand name "LC-20AD" (manufactured by Shimadzu Corporation)
Column: Shodex KF-801 × 2, KF-802, and KF-803 (manufactured by Showa Denko KK)
Measurement temperature: 40 ° C
Eluent: THF, sample concentration 0.1 to 0.2% by weight
Flow rate: 1 mL / min Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation)
Molecular weight: Standard polystyrene equivalent

  Examples of the structure of the fluorine-containing epoxy-modified silsesquioxane of the present invention include a ladder structure, a cage structure (complete cage structure, incomplete cage structure), a random type, and the like. The structure of the fluorine-containing epoxy-modified silsesquioxane can be confirmed from the FT-IR spectrum measurement and the molar ratio of T3 body to T2 body [T3 body / T2 body].

The fluorine-containing epoxy-modified silsesquioxane of the present invention hydrolyzes and condenses a hydrolysable trifunctional silane compound (for example, a compound represented by the following formula (t)) corresponding to a siloxane constituting unit constituting the same. It can be manufactured by attaching to.
RSi (X) ₃ (t)
(Wherein, R represents the R ¹ , R ² or R ^3. X is the same or different and represents an alkoxy group or a halogen atom)

  The ratio of each siloxane structural unit in the fluorine-containing epoxy-modified silsesquioxane of the present invention can be appropriately adjusted by controlling the composition of the raw material (hydrolyzable trifunctional silane) for forming these structural units. .

  Ratio of the trifunctional silane compound corresponding to the siloxane structural unit (T-1) to the trifunctional silane compound corresponding to the siloxane structural unit (T-2) in the total amount (100 mol%) of the hydrolyzable silane compound to be used The proportion of the total amount) is not particularly limited, but is 80 mol% or more, preferably 85 mol% or more, and particularly preferably 90 mol% or more. The upper limit is 100 mol%.

  Also, the hydrolysis and condensation reactions of the trifunctional silane compound corresponding to the siloxane structural unit (T-1) and the trifunctional silane compound corresponding to the siloxane structural unit (T-2) can be performed simultaneously or sequentially It can also be done. When the above reactions are carried out sequentially, the order in which the reactions are carried out is not particularly limited.

  The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably performed in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate, ethyl acetate Esters such as isopropyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol Etc. These can be used singly or in combination of two or more. Among the above solvents, ketones and / or ethers are preferable.

  The amount of the solvent used is not particularly limited, and can be appropriately adjusted according to the reaction time and the like within the range of 2000 parts by weight or less with respect to 100 parts by weight of the total amount of the hydrolyzable silane compound.

  The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably allowed to proceed in the presence of a catalyst and water. As said catalyst, an acid catalyst and an alkali catalyst are mentioned. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, p -Sulfonic acids such as toluene sulfonic acid; Solid acids such as activated clay; Lewis acids such as iron chloride and the like. Examples of the alkali catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide Hydroxides; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and cesium hydrogen carbonate Bicarbonates of alkali metals such as, for example; organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate, cesium acetate (for example, acetates); organic acid salts of alkaline earth metals such as magnesium acetate (for example, Acetates); lithium methoxide, sodium methoxide, sodium ether Alkali metal alkoxides such as sodium isopropoxide, potassium ethoxide and potassium t-butoxide; phenoxides of alkali metals such as sodium phenoxide; triethylamine, N-methylpiperidine, 1,8-diazabicyclo [5.4.0] Amides such as undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene (tertiary amines etc.); pyridine, 2,2'-bipyridyl, 1,10-phenanthroline etc. And nitrogen-containing aromatic heterocyclic compounds of the following. These can be used singly or in combination of two or more. The catalyst can also be used in the state of being dissolved or dispersed in water, a solvent or the like.

  The amount of the catalyst used is not particularly limited, and is, for example, 0.002 to 0.200 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound, and can be appropriately adjusted within this range.

  The amount of water used in the above hydrolysis and condensation reactions is not particularly limited, and is, for example, 0.5 to 20 moles, per 1 mole of the total of hydrolyzable silane compounds, and can be appropriately adjusted within this range. Can.

  The method of adding water is not particularly limited, and the entire amount (total use amount) of water to be used may be added at once or may be added sequentially. When adding sequentially, you may add continuously and may add intermittently.

  Although the reaction temperature of the said hydrolysis and condensation reaction is not specifically limited, 15-100 degreeC is preferable, More preferably, it is 20-80 degreeC. By controlling the reaction temperature within the above range, the degree of polymerization tends to be improved. Moreover, the reaction time of the said hydrolysis and condensation reaction is although it does not specifically limit, 0.1 to 10 hours are preferable, More preferably, it is 1 to 8 hours. Further, the above-mentioned hydrolysis and condensation reaction can be carried out under normal pressure or can be carried out under pressure or under reduced pressure. In addition, the atmosphere at the time of performing the said hydrolysis and condensation reaction is not specifically limited, For example, under inert gas atmospheres, such as nitrogen atmosphere and argon atmosphere, oxygen presence, such as under air, etc. may be any, etc. However, under inert gas atmosphere is preferable.

In addition, as a method for producing the fluorine-containing epoxy-modified silsesquioxane of the present invention, a trifunctional silane compound [R ¹ Si (X) ₃ ] corresponding to the siloxane structural unit (T-1) and a siloxane structural unit (T-2) Described a method for hydrolyzing and condensing a hydrolyzable silane compound containing at least a trifunctional silane compound [R ² Si (X) ₃ ] corresponding to the above), but the production of the fluorine-containing epoxy-modified silsesquioxane of the present invention The method is not limited to this method. For example, in place of the above [R ¹ Si (X) ₃ ], [R ^x Si (X) ₃ ] (R ^{x is a} substituted or unsubstituted alkenyl group) The compound represented may be produced by a hydrolysis and condensation reaction, followed by reaction with an oxidizing agent such as peracid to epoxidize.

  Since the fluorine-containing epoxy-modified silsesquioxane of the present invention has the above-mentioned constitution, by adding it to the curable composition, it is possible to exhibit the effect of improving the scratch resistance of the obtained cured product. Therefore, the fluorine-containing epoxy-modified silsesquioxane of the present invention can be suitably used as a scratch resistance imparting agent and the like.

[Curable composition]
The curable composition of the present invention is a curable composition containing the above-mentioned fluorine-containing epoxy-modified silsesquioxane as an essential component. The curable composition of the present invention can contain the above-mentioned fluorine-containing epoxy-modified silsesquioxane singly or in combination of two or more. The curable composition of the present invention further comprises a curable compound other than the above-mentioned fluorine-containing epoxy-modified silsesquioxane (hereinafter sometimes referred to as "other curable compound"), a polymerization initiator (in particular photo cationic polymerization) Initiators), surface conditioners, surface modifiers and the like may be included.

  The content (compounding amount) of the fluorine-containing epoxy-modified silsesquioxane in the total amount (100% by weight) of the curable compound contained in the curable composition of the present invention is, for example, 0.1% by weight or more, preferably 0. It is 1 to 10% by weight, more preferably 0.5 to 10% by weight, particularly preferably 0.5 to 5% by weight, and most preferably 0.5 to 3% by weight. By containing 0.1% by weight or more of the above-mentioned fluorine-containing epoxy-modified silsesquioxane, a cured product having excellent scratch resistance can be obtained. Moreover, the hardened | cured material excellent in transparency is obtained by containing the said fluorine-containing epoxy modified silsesquioxane in 10 weight% or less.

  As other curable compounds, known or commonly used cationic curable compounds can be used and are not particularly limited. For example, epoxy compounds other than the fluorine-containing epoxy-modified silsesquioxane of the present invention (“other epoxy compounds Compounds), oxetane compounds, vinyl ether compounds, etc. may be mentioned. These can be used individually by 1 type or in combination of 2 or more types.

The curable composition of the present invention contains, as another curable compound, a compound having a 5% weight loss temperature (Td ₅ ) of, for example, 280 ° C. or higher (preferably 300 ° C. or higher, particularly preferably 350 ° C. or higher). It is preferable from the viewpoint that a cured product excellent in heat resistance can be formed and a hard coat layer excellent in heat resistance can be formed. The 5% weight loss temperature of the curable compound can be measured by TG / DTA.

  As other epoxy compounds, known or commonly used compounds having one or more epoxy groups (oxirane ring) in the molecule can be used, and it is not particularly limited. For example, epoxy modified siloxane compounds, alicyclic epoxy compounds And aromatic epoxy compounds and aliphatic epoxy compounds.

  As said epoxy modified siloxane compound, an epoxy modified silicone, an epoxy modified silsesquioxane etc. can be mentioned, for example. These can be used singly or in combination of two or more.

  The epoxy-modified silicone is a compound in which an epoxy group (for example, a glycidyl group, an alicyclic epoxy group, etc.) is introduced into at least one of the terminal and the side chain of the dimethylsilicone skeleton.

The epoxy-modified silsesquioxane is a polysiloxane compound having a silsesquioxane structure (ladder structure, cage structure (complete cage structure, incomplete cage structure), random type, etc.) and an epoxy group bonded thereto, for example, , T unit (especially, T3 form), the following formula (T-1)
[R ¹ SiO _3/2 ] (T-1)
[Wherein, R ¹ represents a group containing an epoxy group]
And a siloxane structural unit (T-1) represented by the following formula (T-3)
[R ³ SiO _3/2 ] (T-3)
[Wherein, R ³ represents a hydrogen atom or a hydrocarbon group which may have a substituent (excluding a halogen atom and an epoxy group)]
And compounds having the siloxane structural unit (T-3) represented by

The examples of R ¹ in the formula (T-1) and R ³ in the formula (T-3) can all be the same as described above.

The epoxy-modified silsesquioxane may have a siloxane structural unit represented by the following formula as a T unit (in particular, a T2 form).
[R ¹ SiO _2/2 (OR ⁴ )] (T-1 ')
[R ³ SiO _2/2 (OR ⁴ )] (T-3 ')
(Wherein, R ¹ , R ³ and R ⁴ are the same as above)

  The epoxy-modified silsesquioxane may have one or more M units, D units, and Q units in addition to T units.

  The [T3 body / T2 body] in the epoxy-modified silsesquioxane is preferably 5 or more from the viewpoint of excellent crack resistance.

  Although the number average molecular weight (Mn) of standard polystyrene conversion by gel permeation chromatography of the said epoxy modified silsesquioxane is not specifically limited, 500-4000 are preferable, More preferably, 1000-2500, More preferably, 1100-2600 It is. When the number average molecular weight is 1,000 or more, the resulting cured product tends to be excellent in the abrasion resistance, heat resistance and adhesiveness. In addition, the heat resistance and adhesiveness of the cured product of the curable composition tend to be improved. On the other hand, when the number average molecular weight is 4000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product tends to be improved.

  Although the molecular weight dispersion degree (Mw / Mn) of standard polystyrene conversion by gel permeation chromatography of the said epoxy modified silsesquioxane is not limited, 3.0 or less (for example, 1.0-3.0) is preferable More preferably, it is 1.1-2.0, More preferably, it is 1.1-1.5.

  The epoxy-modified silsesquioxane can be produced by subjecting a hydrolyzable trifunctional silane compound corresponding to a siloxane constitutional unit constituting the same to hydrolysis and condensation reactions.

Examples of the above-mentioned alicyclic epoxy compound include known and commonly used compounds having one or more alicyclic groups and one or more epoxy groups in the molecule, and are not particularly limited. For example, the following compounds may be mentioned. .
(1) Compound having an epoxy group (referred to as "alicyclic epoxy group") composed of two adjacent carbon atoms constituting an alicyclic ring and oxygen atom in the molecule (2) An epoxy group is directly on the alicyclic ring Compound (3) having a single bond and a compound having an alicyclic and glycidyl ether group in the molecule (glycidyl ether type epoxy compound)

As a compound which has an alicyclic epoxy group in the said (1) molecule | numerator, the compound represented by following formula (i) is mentioned.

  In said Formula (i), Y shows a single bond or a coupling group (bivalent group which has one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which a part or all of carbon-carbon double bonds are epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. And the like. In addition, substituents, such as an alkyl group, may be couple | bonded with one or more of the carbon atom which comprises the cyclohexane ring (cyclohexene oxide group) in Formula (i).

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. As a C1-C18 linear or branched alkylene group, a methylene group, a methyl methylene group, dimethyl methylene group, ethylene group, a propylene group, trimethylene group etc. are mentioned, for example. Examples of the divalent alicyclic hydrocarbon group include a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, and a 1,3-disubstituted cycloaliphatic hydrocarbon group. Cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group and the like can be mentioned.

  The alkenylene group in the above-mentioned alkenylene group (sometimes referred to as “epoxidized alkenylene group”) in which part or all of the carbon-carbon double bond is epoxidized is, for example, vinylene group, propenylene group, 1-butenylene group And C2-C8 linear or branched alkenylene groups such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like. In particular, as the above-mentioned epoxidized alkenylene group, an alkenylene group in which all of carbon-carbon double bonds are epoxidized is preferable, and more preferably, all of carbon-carbon double bonds have 2 to 4 carbon atoms having epoxidized all of carbon-carbon double bonds. It is an alkenylene group.

Representative examples of the alicyclic epoxy compound represented by the above formula (i) include (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexan-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexan-1-yl) propane, 1,2-bis ( Examples thereof include 3,4-epoxycyclohexan-1-yl) ethane, compounds represented by the following formulas (i-1) to (i-10), and the like. R 'in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and in particular, a linear chain having 1 to 3 carbon atoms such as methylene, ethylene, propylene, and isopropylene. Or branched alkylene groups are preferred. Further, n ^{1 to} n ⁸ in the following formulas (i-5), (i-7), (i-9) and (i-10) each represent an integer of 1 to 30.

As a compound which the epoxy group has couple | bonded with the above-mentioned (2) alicyclic ring directly by single bond, the compound etc. which are represented by following formula (ii) are mentioned, for example.

In formula (ii), R ′ ′ is a group (p-valent organic group) obtained by removing p hydroxyl groups (—OH) from the structural formula of p-valent alcohol, and p and n ⁹ each represent a natural number. Examples of the p-valent alcohol [R ′ (OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (alcohols having 1 to 15 carbon atoms, etc.), and the like. p is preferably 1 to 6, n ⁹ is preferably 1 to 30. When p is 2 or more, n ⁹ in each of the groups in [] (in the outer square brackets) may be the same or different. Specific examples of the compound represented by the above formula (ii) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, And trade name "EHPE 3150" (manufactured by Daicel Co., Ltd.) and the like.

  Examples of the compound having an alicyclic and glycidyl ether group in the (3) molecule described above include glycidyl ethers of alicyclic alcohols (particularly, alicyclic polyhydric alcohols). More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy)] Compound (hydrogenated bisphenol A epoxy compound) obtained by hydrogenating a bisphenol A epoxy compound such as cyclohexyl] propane; bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2, 2, Compound obtained by hydrogenating a bisphenol F-type epoxy compound such as 3-epoxypropoxy) cyclohexyl] methane (hydrogenated bisphenol F-type epoxy compound Hydrogenated biphenol type epoxy compound; hydrogenated phenol novolac type epoxy compound; hydrogenated cresol novolac type epoxy compound; hydrogenated cresol novolac type epoxy compound of bisphenol A; hydrogenated naphthalene type epoxy compound; epoxy compound obtained from trisphenolmethane And the like.

  Examples of the compound having an alicyclic and glycidyl ether group in the (3) molecule described above include glycidyl ethers of alicyclic alcohols (particularly, alicyclic polyhydric alcohols). More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy)] Compound (hydrogenated bisphenol A epoxy compound) obtained by hydrogenating a bisphenol A epoxy compound such as cyclohexyl] propane; bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2, 2, Compound obtained by hydrogenating a bisphenol F-type epoxy compound such as 3-epoxypropoxy) cyclohexyl] methane (hydrogenated bisphenol F-type epoxy compound Hydrogenated biphenol type epoxy compound; hydrogenated phenol novolac type epoxy compound; hydrogenated cresol novolac type epoxy compound; hydrogenated cresol novolac type epoxy compound of bisphenol A; hydrogenated naphthalene type epoxy compound; epoxy compound obtained from trisphenolmethane Hydrogenated epoxy compounds; hydrogenated epoxy compounds of the following aromatic epoxy compounds, and the like.

  As the above-mentioned aromatic epoxy compound, for example, an epi-bis-type glycidyl ether type epoxy resin obtained by condensation reaction of bisphenols [eg bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol etc.] with epihalohydrin; High molecular weight epi-bis-type glycidyl ether type epoxy resin obtained by further addition reaction of bis-type glycidyl ether type epoxy resin with the above-mentioned bisphenol; phenols [eg phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] and aldehydes [eg, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylic acid Novolak alkyl type glycidyl ether type epoxy resin obtained by further condensation reaction of polyhydric alcohol obtained by condensation reaction with aldehyde etc. with epihalohydrin; two phenol skeletons bonded to position 9 of fluorene ring And the epoxy compound etc. which the glycidyl group has couple | bonded directly or via the alkylene oxy group to the oxygen atom which remove | eliminated the hydrogen atom from the hydroxyl group of these phenol frame | skeleton are mentioned, respectively.

  Examples of the aliphatic epoxy compounds include glycidyl ethers of alcohols having no q-valent cyclic structure (q is a natural number); monohydric or polyhydric carboxylic acids [eg, acetic acid, propionic acid, butyric acid, stearic acid, Glycidyl esters of adipic acid, sebacic acid, maleic acid, itaconic acid etc.]; Epoxides of fats and oils with double bonds such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil etc. Polyolefins such as epoxidized polybutadiene Epoxides of alkadiene are included. Examples of the above-mentioned alcohol having no q-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol and 1-butanol; ethylene glycol, 1,2-propanediol, 1 And a dihydric alcohol such as 3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and the like; And trivalent or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. That. Also, the q-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol or the like.

  Examples of the oxetane compounds include known and commonly used compounds having one or more oxetane rings in the molecule, and are not particularly limited. For example, 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3- (Hydroxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane Ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-) Oxetanyl)] methyl} ether, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bisi Clohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] cyclohexane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- {[(3-Ethyl oxetan-3-yl) methoxy] methyl)} oxetane, xylylene bis oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanyl silsesquioxane And phenol novolac oxetane.

  As the vinyl ether compound, known or commonly used compounds having one or more vinyl ether groups in the molecule can be used, and although not particularly limited, for example, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxy Propyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy isopropyl vinyl ether, 4-hydroxy butyl vinyl ether, 3-hydroxy butyl vinyl ether, 2-hydroxy butyl vinyl ether, 3-hydroxy isobutyl vinyl ether, 2-hydroxy isobutyl vinyl ether, 1-methyl-3 -Hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethyl propyl vinyl ether 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexane dimethanol monovinyl ether, 1,4-cyclohexane Methanol divinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexane dimethanol divinyl ether, 1,2-cyclohexane dimethanol monovinyl ether, 1,2-cyclohexane dimethanol divinyl ether, p-xylene glycol monovinyl ether P-xylene glycol divinyl ether, m-xylene glycol monovinyl ether, m-xylene glycol divinyl ether, o-xylene Glycol monovinyl ether, o-xylene glycol divinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, penta Ethylene glycol monovinyl ether, pentaethylene glycol divinyl ether, oligoethylene glycol monovinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol Cole divinyl ether, tripropylene glycol monovinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol monovinyl ether, tetrapropylene glycol divinyl ether, pentapropylene glycol monovinyl ether, pentapropylene glycol divinyl ether, oligopropylene glycol monovinyl ether, oligopropylene glycol di Vinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, isosorbide divinyl ether, oxanorbornene divinyl ether, phenyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, Droquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroxyoxa norbornane methanol divinyl ether, 4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether and the like.

  Content (compounding amount) of other curable compounds (particularly, other epoxy compounds, particularly epoxy modified siloxane compound and alicyclic epoxy compound) in the total amount (100% by weight) of the curable compound contained in the curable composition of the present invention Is, for example, 90 to 99.5% by weight, preferably 95 to 99.5% by weight, particularly preferably 97 to 99.5% by weight. Desired performance (for example, rapid curability, viscosity adjustment, etc.) may be able to be provided by mix | blending another curable compound in the said range.

  In addition, fluorine-containing epoxy-modified silsesquioxane and the other epoxy compounds (particularly, epoxy-modified siloxane compounds and alicyclic epoxy compounds) in the total amount (100% by weight) of the curable compound contained in the curable composition of the present invention The proportion of the total content is, for example, 70% by weight or more, preferably 80% by weight or more, particularly preferably 90% by weight or more, and particularly preferably 95% by weight or more. The upper limit is 100% by weight.

(Cationic polymerization initiator)
It is preferable that the curable composition of the present invention contains one or more cationic polymerization initiators in that it can achieve quick curing and shorten the curing time until tack-free. The cationic polymerization initiator includes a photo cationic polymerization initiator and a thermal cationic polymerization initiator, and among them, it is preferable to contain a photo cationic polymerization initiator.

  The cationic photopolymerization initiator is a compound that generates an acid upon irradiation with light to initiate a curing reaction of the cationically curable compound contained in the curable composition, and is a cationic part that absorbs light and a source of the acid. Of the anion moiety The cationic photopolymerization initiators can be used alone or in combination of two or more.

  Examples of the cationic photopolymerization initiator include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salt compounds, etc. Can be mentioned. In the present invention, among them, it is preferable to use an iodonium salt compound and / or a sulfonium salt compound.

As a cation part of an iodonium salt type compound, the bis [4-n-alkyl ( _C10-13 ) phenyl] iodonium ion etc. can be mentioned, for example.

  Examples of the cation part of the sulfonium salt compound include (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, 4- (4-biphenylylthio) phenyl Examples include arylsulfonium ions such as -4-biphenylylphenylsulfonium ion and tri-p-tolylsulfonium ion (particularly, triarylsulfonium ion).

The anionic portion of the cationic photopolymerization initiator, for _{example, [(Z) s B (} Phf) 4-s] - ( wherein, Z is .Phf illustrating a phenyl group or a biphenylyl group is at least one hydrogen atom, Represents a phenyl group substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom, s is an integer of 0 to 3), BF ₄ ⁻ , [(R f) _t PF ^_6-t] - (Rf: alkyl group in which at least 80% are substituted with fluorine atoms of the hydrogen atom, t: 0 to 5 ^{_{integer), AsF 6 -, SbF 6}} - and the like, etc. ^-, SbF ₅ OH it can.

As a photocationic polymerization initiator, For example, bis [4-n-alkyl (C _10-13 ) phenyl] iodonium tetrakis (pentafluorophenyl) borate, (4-hydroxyphenyl) methyl benzyl sulfonium tetrakis (pentafluorophenyl) borate 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate, [4- (4-biphenyl] Rylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenylsulfonium] hexafluoroantimone Diphenyl [4- (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexame Fluorophosphate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide phenyltris (pentafluorophenyl) borate , [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonyl sulfonium phenyltris (pentafluorophenyl) vole , Trade names “Cyracure UVI-6970”, “Cyracure UVI-6974”, “Cyracure UVI-6990”, “Cyracure UVI-950” (all manufactured by Union Carbide Corporation), “Irgacure 250”, “Irgacure 261”, “Irgacure264” (Above, BASF Corporation), "CG-24-61" (Ciba Geigy Corporation), "Optomer SP-150", "Optomer SP-151", "Optomer SP-170", "Optomer SP-171" ( As described above, manufactured by ADEKA Co., Ltd., “DAICAT II” (manufactured by Daicel Co., Ltd.), “UVAC 1590”, “UVAC 1591” (manufactured by Daicel Cytech Co., Ltd.), “CI-2064”, “CI-2639 "," CI-2624 "," CI-2481 " “CI-2734”, “CI-2855”, “CI-2823”, “CI-2758”, “CIT-1682” (all manufactured by Nippon Soda Co., Ltd.), “PI-2074” (manufactured by Rhodia, Inc.) Tetrakis (pentafluorophenyl) borate tolkyumil iodonium salt), "FFC 509" (manufactured by 3M company), "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS -103 "," MDS-103 "," DTS-103 "," NAT-103 "," NDS-103 "(above, Midori Chemical Co., Ltd. product)," CD-1010 "," CD-1011 ", Commercial products such as “CD-1012” (above, Sartomer, USA), “CPI-100P”, and “CPI-101A” (above, San-Apro Ltd.) can be used. .

  The content of the cationic polymerization initiator is not particularly limited, but is preferably 0.01 to 3.0 parts by weight, and more preferably 0.2 parts by weight with respect to 100 parts by weight of the cationic curable compound contained in the curable composition. It is preferably 0.5 to 3.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, and particularly preferably 0.3 to 0.8 parts by weight. By setting the content of the cationic polymerization initiator to 0.01 parts by weight or more, the curing reaction can be efficiently and sufficiently progressed, and a cured product having excellent scratch resistance can be obtained. On the other hand, when the content of the cationic polymerization initiator is 3.0 parts by weight or less, the storage stability of the curable composition can be improved, and the coloring of the cured product can be suppressed.

(Leveling agent)
In the curable composition of the present invention, the inclusion of a leveling agent can impart surface smoothness and adhesion to the obtained cured product, and the effect of further improving the scratch resistance can be obtained. preferable. As a leveling agent, a silicone type leveling agent, a fluorine type leveling agent, etc. can be mentioned. These can be used singly or in combination of two or more. In the present invention, among these, a fluorine-based leveling agent is preferable in that it can impart particularly excellent surface smoothness.

  The fluorine-based leveling agent includes a compound having a perfluoroalkyl group and a compound having a poly (perfluoroalkylene ether) chain.

Examples of the perfluoroalkyl group in the compound having a perfluoroalkyl group include perfluoroC _1-10 alkyl groups such as trifluoromethyl, pentafluoroethyl, hexafluoropropyl, heptafluoroisopropyl and the like.

The poly (perfluoro alkylene ether) chain in the compound having the poly (perfluoro alkylene ether) chain is, for example, represented by the following formula (c), and Y ′ in the formula is, for example, a C _1-10 perfluoroalkylene group Specifically, groups represented by the following formulas (1) to (5) can be mentioned.

  The plurality of Y's in the formula (c) may be identical to or different from each other. Moreover, t 'in Formula (c) is a number (polymerization degree) of repetition of a perfluoro alkylene ether unit, for example, 10-3000, preferably 30-1000, more preferably 50-500.

  The fluorine-based leveling agent has, for example, a hydrophilic group, a lipophilic group, a reactive group for an epoxy group, a radically polymerizable group, etc., in addition to the perfluoroalkyl group or the poly (perfluoroalkylene ether) chain. May be

  Examples of the hydrophilic group include a sulfonic acid group, a sulfuric acid ester group, a phosphoric acid ester group, a polyethylene oxide chain, and a hydroxyl group.

  As said lipophilic group, a hydrocarbon group, an ether group, ester group etc. can be mentioned, for example.

  Examples of the reactive group for the epoxy group include a hydroxyl group, an amino group, a carboxyl group, an acid anhydride group (maleic anhydride group etc.), an isocyanate group and the like.

  As said radically polymerizable group, a (meth) acryloyloxy group, a vinyl group etc. can be mentioned, for example.

  As the fluorine-based leveling agent, for example, trade names “Optool DSX”, “Optool DAC-HP” (all manufactured by Daikin Industries, Ltd.); trade names “Surflon S-242”, “Surflon S-243”, "Surflon S-420", "Surflon S-611", "Surflon S-651", "Surflon S-386" (above, AGC Seimi Chemical Co., Ltd. product); Brand name "BYK-340" (Bick Chemie Japan) (Product name) "AC 110a", "AC 100a" (all, Algin Chemie product); trade name "Megafuck F-114", "Megafuck F-410", "Megafuck F-444" "Megafuck EXP TP-2066", "Megafuck F-430", "Megafuck F-472SF", "MegaFat "F-477", "Megafuck F-552", "Megafuck F-553", "Megafuck F-554", "Megafuck F-555", "Megafuck R-94", "Megafuck RS" -72-K "," Megafuck RS-75 "," Megafuck RS-90 "," Megafuck F-556 "," Megafuck EXP TF-1367 "," Megafuck EXP TF-1437 "," Megafuck Fuck F-558 "," Megafuck EXP TF-1537 "(all, DIC Corporation); trade name" FC-4430 "," FC-4432 "(Sumitomo 3M Corp.); trade name "Futagent 100", "Futagent 100C", "Futagent 110", "Futagent 150", "Futagent 150CH", "Futagent 150" Agent AK, "Futagent 501," "Futagent 250," "Futagent 251," "Futagent 222F," "Futagent 208G," "Futagent 300," "Futagent 310", "Futagent Genent 400 SW "(all manufactured by Neos Co., Ltd.); trade names" PF-136A "," PF-156A "," PF-151N "," PF-636 "," PF-6320 "," PF-656 " Commercial products, such as "PF-6520", "PF-651", "PF-652", and "PF-3320" (above, Kitamura Chemical Industrial Co., Ltd. product) can be used.

  The amount of the leveling agent used (the total amount of two or more types used) is, for example, 0.1 to 2.0 parts by weight with respect to 100 parts by weight of the cationically curable compound. When the leveling agent is used in the above range, the scratch resistance of the resulting cured product can be improved. On the other hand, when the amount of the leveling agent used is excessive, the surface hardness of the cured product tends to decrease.

(solvent)
The curable composition of the present invention may further contain a solvent. Examples of the solvent include water, organic solvents and the like, which can dissolve the fluorine-containing epoxy-modified silsesquioxane of the present invention, and the additives used as needed, and do not inhibit the polymerization There is no particular limitation as long as

  It is preferable to use a solvent which can impart fluidity suitable for application by spin coating and can be easily removed by heating at a temperature at which the progress of polymerization can be suppressed, and the boiling point (1 One or more solvents (for example, toluene, butyl acetate, methyl isobutyl ketone (MIBK), xylene, mesitylene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, etc.) at 170 ° C. or less at atmospheric pressure are used It is preferable to do.

  It is preferable to use the solvent in the range where the concentration of non-volatile components contained in the curable composition is, for example, about 30 to 80% by weight, preferably 40 to 70% by weight, particularly preferably 50 to 60% by weight. It is preferable at the point which can provide coating property. If the amount of the solvent used is excessive, the viscosity of the curable composition tends to be low, and it tends to be difficult to form a layer having an appropriate film thickness (for example, about 0.5 to 30 μm). On the other hand, when the amount of the solvent used is too small, the viscosity of the curable composition may be too high, and it may be difficult to uniformly apply the composition to a support or an adherend.

  The curable composition of the present invention further comprises, as an optional component, an inorganic filler (precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide , Calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride, etc.) or those obtained by surface treating these inorganic fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, organosilazanes, etc., fine powders of organic resins (Fine powder of silicone resin, epoxy resin, fluoro resin etc.) Conductive metal powder (powder of silver, copper etc.), curing agent (amine curing agent, polyaminoamide curing agent, acid anhydride curing agent, phenol Curing agents etc.), curing assistants, curing accelerators (imidazoles, alkali metals or alkaline earth metal alkoxides , Phosphines, amide compounds, Lewis acid complex compounds, sulfur compounds, boron compounds, condensable organic metal compounds, etc., stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, heavy metal free) Activators, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcements (other fillers etc.), nucleating agents, coupling agents, lubricants, Waxes, plasticizers, mold release agents, impact modifiers, hue modifiers, clarifying agents, rheology modifiers (such as flow improvers), processability modifiers, colorants (such as dyes and pigments), antistatic agents , Dispersants, surface modifiers (slip agents etc.), matting agents, antifoaming agents, foam inhibitors, defoamers, antibacterial agents, preservatives, viscosity modifiers, thickeners, photosensitizers, foaming One or more agents may be contained. The content (the total amount of two or more components) of the above optional components is, for example, 10% by weight or less, preferably 5% by weight or less, particularly preferably 1% by weight or less of the total amount of the curable composition of the present invention is there.

  The curable composition of the present invention can be prepared by stirring and mixing the above-mentioned components at room temperature or while heating as required.

  The curable composition of the present invention is not particularly limited, but is preferably liquid at normal temperature (about 25 ° C.). The viscosity of the curable composition of the present invention is preferably adjusted according to the film thickness at the time of coating by spin coating, for example, 1 to 5000 mPa · s when coated at a film thickness of 0.1 to 50 μm. It is preferable to set it as s. When the viscosity of the curable composition of the present invention is within the above range, for example, it becomes easy to form a coating film having a uniform film thickness on the surface of a substrate or the like. The viscosity of the curable composition of the present invention was measured using a viscometer (trade name "MCR301", manufactured by Anton Paar Co., Ltd.), with a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature: Measured under conditions of 25 ° C.

[Cured product]
By advancing the polymerization reaction of the cationic curable compound contained in the curable composition of the present invention, the curable composition can be cured, and a cured product ("the cured product of the present invention" may be referred to) ) Can be obtained. The method of curing can be appropriately selected from known methods, and is not particularly limited, but a method of irradiating active energy rays is preferable. As the active energy ray, any of infrared ray, visible light, ultraviolet ray, X-ray, electron beam, α-ray, β-ray, γ-ray and the like can be used, for example. Among them, ultraviolet light is preferable in terms of excellent handleability.

The conditions for curing the curable composition of the present invention by irradiation with active energy rays (such as irradiation conditions with active energy rays) depend on the type and energy of the active energy ray to be irradiated, the shape and size of the cured product, etc. Although it can adjust suitably and it does not specifically limit, When irradiating an ultraviolet-ray, it is preferable to set it as about 1-1000 mJ / cm < ² >, for example. For irradiation with active energy rays, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser or the like can be used. After irradiation with active energy rays, heat treatment (annealing, aging) can be further performed to further promote the curing reaction.

  The cured product of the present invention is excellent in abrasion resistance. Therefore, the curable composition of the present invention can be suitably used as a hard coating agent.

[Hard coat film]
The hard coat film of the present invention is characterized by comprising a cured film of the above-mentioned curable composition (that is, a film composed of a cured product of the above-mentioned curable composition). The hard coat film of the present invention preferably has a configuration in which a cured film of the curable composition is laminated on at least one surface of a substrate. Accordingly, the hard coat film of the present invention preferably comprises a base layer and a hard coat layer comprising a cured film of the above-mentioned curable composition. The hard coat film of the present invention may have only one base layer and one hard coat layer, or may have two or more layers. The hard coat film of the present invention may also be provided with layers other than the base layer and the hard coat layer (for example, an undercoat layer, an adhesive layer, an intermediate layer, etc.).

  A well-known and commonly used substrate (a substrate used for an adhesive sheet) can be used as the substrate, and is not particularly limited. For example, plastic substrates, metal substrates, ceramic substrates, semiconductor substrates , Glass substrates, paper substrates, wood substrates, substrates whose surfaces are coated surfaces, and the like. In addition, the thickness of the substrate (in the case of having two or more layers, the total thickness thereof) can be appropriately selected, for example, in the range of 1 to 1000 μm.

  In the hard coat film of the present invention, the curable composition is applied to at least one surface of the substrate, dried if necessary, and the curable composition is further cured by irradiation of active energy rays or the like. It can be manufactured by The method of application is not particularly limited, and known means may be used. Further, the means and conditions for drying are not particularly limited, and conditions capable of removing volatile matter such as solvent can be set as much as possible, and well-known and commonly used means can be used.

  The thickness of the cured film (that is, the hard coat layer) in the hard coat film of the present invention is, for example, about 1 to 100 μm, and the lower limit is preferably 3 μm, particularly preferably 5 μm, most preferably 8 μm, particularly preferably 10 μm. is there. The upper limit is preferably 70 μm, particularly preferably 50 μm, and most preferably 30 μm.

  The total thickness of the hard coat film of the present invention is, for example, about 10 to 400 μm, and the lower limit is preferably 30 μm, particularly preferably 50 μm, most preferably 100 μm, and particularly preferably 150 μm. Also, the upper limit is preferably 300 μm, particularly preferably 250 μm, particularly preferably 200 μm.

  The hard coat film of the present invention is excellent in scratch resistance because it comprises the cured film of the curable composition as a hard coat layer, and the degree of change in haze (ΔHz) according to the steel wool durability test (1000 times) is, for example, 0.1. % Or less, particularly preferably 0.05% or less, and the degree of change in haze (ΔHz) according to the steel wool durability test (2000 times) is, for example, 0.5% or less.

  In addition, the hard coat layer of the hard coat film of the present invention is a cured film of the above curable composition, and therefore it is excellent in transparency. Is preferably at most 0.7%, particularly preferably at most 0.5%, most preferably at most 0.3%.

  Since the hard coat film of the present invention has the above-mentioned properties, it can be suitably used for preventing scratches on various displays and touch panels such as liquid crystal televisions, liquid crystal monitors, notebook computers, mobile displays, tablet PCs and smartphones. .

EXAMPLES The present invention will be described in more detail based on examples given below, but the present invention is not limited by these examples. In addition, the measurement of the molecular weight of a product can be performed using Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskgel GMH _HR- M × 2 (manufactured by Tosoh Corp.), guard column: Tskgel guard column (manufactured by Tosoh (Ltd.)) H _HR L, column oven: cOLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measuring conditions: 40 ° C., the molecular weight was performed by standard polystyrene. Moreover, the measurement of the molar ratio [T3 body / T2 body] of T2 body and T3 body in a product was performed by ²⁹ Si-NMR spectrum measurement by JEOL ECA500 (500 MHz).

Preparation Example 1 [Production of Epoxy-Modified Silsesquioxane]
In a 300 mL flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, 161.5 millimoles (39 of 39) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane under a nitrogen stream. 79 g), 9 mmol (1.69 g) of phenyltrimethoxysilane, and 165.9 g of acetone were charged, and the temperature was raised to 50.degree. To the mixture thus obtained, 4.70 g of a 5% aqueous solution of potassium carbonate (1.7 mmol as potassium carbonate) was added dropwise over 5 minutes, and then 1700 mmol (30.60 g) of water was added dropwise over 20 minutes did. Note that no significant temperature rise occurred during the dropping. Thereafter, the polycondensation reaction was performed for 4 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
When the product in the reaction solution after the polycondensation reaction was subjected to GPC measurement, the number average molecular weight was 1911, and the molecular weight dispersion degree was 1.47. The ratio of T2 body to T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the above product was 10.3.
Thereafter, the reaction solution is cooled, washed with water until the lower layer solution becomes neutral, and the upper layer solution is separated, and then the solvent is distilled off from the upper layer solution under the conditions of 1 mmHg and 40 ° C. to form a colorless and transparent liquid (Epoxy-modified silsesquioxane; ESQ, epoxy equivalent weight: 198 g / eq) was obtained. The T _d5 of the above product was 370 ° C.

Example 1 [Production of Fluorine-Containing Epoxy-Modified Silsesquioxane]
A thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube were attached to a 100 mL flask (reaction vessel), and 20.0 mmol of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane under nitrogen stream (4. 93 g), 20 mmol (4.37 g) of 3,3,3-trifluoropropyltrimethoxysilane, 37.32 g of acetone, and 400 mmol (7.2 g) of water were charged, and the temperature was raised to 48 ° C. To the mixture thus obtained, 1.11 g of a 5% aqueous potassium carbonate solution (0.4 mmol as potassium carbonate) was added dropwise over 5 minutes. Note that no significant temperature rise occurred during the dropping. Thereafter, the polycondensation reaction was performed for 5 hours under a nitrogen stream at 48 ° C.
When the product in the reaction solution after the polycondensation reaction was subjected to GPC measurement, the number average molecular weight was about 1400, and the molecular weight dispersion degree was 1.27. The ratio of T2 body to T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum (FIG. 1) of the above product was 23.5. Also shows a ¹ H-NMR (CDCl ₃₎ measurement results of the product in FIG.
Thereafter, the reaction solution is cooled, MIBK is added, water washing is performed until the lower layer solution becomes neutral, the upper layer solution is separated, and then the solvent is distilled off from the upper layer solution under 1 mmHg and 50 ° C. About 10 g of a colorless and transparent liquid product (fluorine-containing epoxy-modified silsesquioxane; FESQ (1), epoxy equivalent weight: 222 g / eq) was obtained, containing about 25% by weight.

Example 2 [Production of Fluorine-Containing Epoxy-Modified Silsesquioxane]
A thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube were attached to a 100 mL flask (reaction vessel), and 20.0 mmol of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane under nitrogen stream (4. 93 g), 1 H, 1 H, 2 H, 2 H-nonafluorohexyl trimethoxysilane 20 mmol (7.37 g), acetone 49.2 g, and water 400 mmol (7.2 g) were charged, and the temperature was raised to 48 ° C. To the mixture thus obtained, 1.10 g of a 5% aqueous solution of potassium carbonate (0.4 mmol as potassium carbonate) was added dropwise over 5 minutes. Note that no significant temperature rise occurred during the dropping. Thereafter, the polycondensation reaction was performed for 5 hours under a nitrogen stream at 48 ° C. Analysis of the product in the reaction solution after the polycondensation reaction revealed that the number average molecular weight was 1550 and the molecular weight dispersity was 1.30. The ratio of T2 body to T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum (FIG. 3) of the above product was 19.4. Also shows a ¹ H-NMR (CDCl ₃₎ measurement results of the product in FIG.
Thereafter, the reaction solution is cooled, MIBK is added, water washing is performed until the lower layer solution becomes neutral, the upper layer solution is separated, and then the solvent is distilled off from the upper layer solution under 1 mmHg and 50 ° C. 12 g of a colorless and transparent liquid product (fluorine-containing epoxy-modified silsesquioxane; FESQ (2), epoxy equivalent weight: 294 g / eq) containing about 25% by weight was obtained.

Example 3
In a 6 mL brown sample bottle, 0.15 g of the product obtained in Example 1 (0.11 g of FESQ (1) +0.04 g of MIBK) and 2.85 g of the product obtained in Preparation Example 1 (ESQ 2.18 g + MIBK0. 67 g), 45.8 mg of WPI-124 (50% solution, containing 22.9 mg of photo cationic polymerization initiator), 0.0114 g of S-243, and 0.502 g of MIBK, mixed by stirring with a vibrator, and cured (Hard coat agent, viscosity at 25 ° C .: 97.5 mPa · s) was prepared.
Using the obtained hard coating agent, a wire bar is used on a PET film (thickness: 188 μm, trade name “A4300”, manufactured by Toyobo Co., Ltd.) so that the thickness of the hard coat layer after curing is 10 μm. After cast coating, it was allowed to stand (prebaked) in an oven at 120 ° C. for 10 minutes and then irradiated with ultraviolet light (irradiation conditions (irradiation amount): 430 mJ / cm ² , irradiation intensity: 120 W / cm ² ). Finally, the coated film of the above hard coating agent was cured by heat treatment (aging) at 80 ° C. for 2 hours to prepare a hard coated film (thickness 198 μm) having a hard coated layer.

Examples 4 to 5, Comparative Example 1
A curable composition (hard coat agent) was produced and a hard coat film was produced in the same manner as in Example 3 except that the formulation (unit: g) was changed as described in Table 1 below.

The abrasion resistance of the hard coat films obtained in Examples and Comparative Examples was evaluated by the following method.
Hard coat layer surface of hard coat film was rubbed with steel wool endurance tester with 1000, 2000 reciprocation (speed 10 cm / s) with load of 2.0 kg / cm ² with steel wool # 0000 of diameter 1.0 cm . The haze of the hard coat film before and after the test was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., NDH-300A), and the scratch resistance was evaluated from the degree of change in haze (Δ Hz). The results are shown in Table 1, FIGS.

FESQ (1): Fluorine-containing epoxy-modified silsesquioxane obtained in Example 1 FESQ (2): Fluorine-containing epoxy-modified silsesquioxane ESQ obtained in Example 2: Epoxy obtained in Preparation Example 1 Modified silsesquioxane WPI-124: Photocationic polymerization initiator, bis [4-n-alkyl (C _10-13 ) phenyl] iodonium tetrakis (pentafluorophenyl) borate, molecular weight 1296.79, Wako Pure Chemical Industries, Ltd. S-243: a fluorine-based leveling agent, trade name "Surflon S-243", AGC Seimi Chemical Co., Ltd. MIBK: methyl isobutyl ketone, solvent

  From Table 1, according to the curable composition containing the fluorine-containing epoxy-modified silsesquioxane of the present invention, it can be understood that excellent scratch resistance can be imparted while maintaining the transparency of the obtained cured product. .

Claims (7)

Following formula (T-1)
[R ¹ SiO _3/2 ] (T-1)
[Wherein, R ¹ represents a group containing an epoxy group]
And a siloxane structural unit (T-1) represented by
Following formula (T-2)
[R ² SiO _3/2 ] (T-2)
[Wherein, R ² represents a group in which two or more hydrogen atoms of an alkyl group having 2 to 16 carbon atoms are substituted with a fluorine atom]
And fluorine-containing epoxy-modified silsesquioxane having a siloxane structural unit (T-2) represented by   The ratio of the total of the siloxane structural unit (T-1) and the siloxane structural unit (T-2) in all the siloxane structural units (100 mol%) constituting the fluorine-containing epoxy-modified silsesquioxane is 80 mol% or more The fluorine-containing epoxy according to claim 1, wherein the molar ratio (the former / the latter) of the siloxane structural unit (T-1) and the siloxane structural unit (T-2) is 90/10 to 10/90. Modified silsesquioxane.   The fluorine-containing epoxy-modified silsesquioxane according to claim 1 or 2, wherein the number average molecular weight (Mn) in terms of standard polystyrene conversion by gel permeation chromatography is 500 to 4000. The group according to any one of claims 1 to 3, wherein R ¹ is at least one group selected from the group consisting of groups represented by the following formulas (1a), (1b), (1c), and (1d) The fluorine-containing epoxy-modified silsesquioxane according to any one of the preceding claims.

[Wherein, R ^1a , R ^1b , R ^1c and R ^1d are the same or different and represent a linear or branched alkylene group]   A curable composition comprising the fluorine-containing epoxy-modified silsesquioxane according to any one of claims 1 to 4.   The curable composition according to claim 5, which is a hard coating agent.   A hard coat film provided with a cured film of the curable composition according to claim 6.

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