JP6530027B2 - Polyorganosilsesquioxane, hard coat film, adhesive sheet and laminate - Google Patents

Description

  The present invention relates to polyorganosilsesquioxane, and a curable composition containing the polyorganosilsesquioxane and a cured product thereof. The present invention also relates to a hard coat film having a hard coat layer formed of the above-mentioned hard coat solution (hard coat agent) containing polyorganosilsesquioxane. The present invention also relates to a composition containing the above polyorganosilsesquioxane (composition for adhesive), and an adhesive sheet and a laminate using the composition.

  Conventionally, a hard coat film having a hard coat layer on one side or both sides of a substrate and having a pencil hardness of about 3 H on the surface of the hard coat layer is distributed. As a material for forming a hard coat layer in such a hard coat film, a UV acrylic monomer is mainly used (see, for example, Patent Document 1). In some cases, nanoparticles are added to the hard coat layer in order to further improve the pencil hardness of the hard coat layer surface.

  On the other hand, glass is known as a material having a very high surface hardness, and in particular, it is known that the pencil hardness of the surface is increased to 9H by alkali ion exchange treatment, but flexibility and processability Because it is poor, it can not be manufactured or processed by the roll-to-roll method, but it is necessary to manufacture or process one by one, resulting in high production cost.

JP, 2009-279840, A

  However, the hard coat film using the above-mentioned UV acrylic monomer can not yet be said to have sufficient surface hardness. In general, it is conceivable to make the UV acrylic monomer polyfunctional or to make the hard coat layer thicker in order to further increase the hardness, but when such a method is adopted, the cure shrinkage of the hard coat layer is As a result, there is a problem that the hard coat film is curled or cracked. In addition, when nanoparticles are added to the hard coat layer, if the compatibility between the nanoparticles and the UV acrylic monomer is poor, there is a problem that the nanoparticles aggregate and the hard coat layer becomes white.

  On the other hand, in the alkali ion exchange treatment of glass, a large amount of alkaline waste liquid is generated, which causes a problem of large environmental load. In addition, glass has the disadvantage of being heavy and fragile, and the disadvantage of high cost. Therefore, there is a demand for an organic material which is excellent in flexibility and processability and which has a high surface hardness.

  Furthermore, the applications in which hard coat films are used are expanding in recent years, and in addition to having high surface hardness as described above, hard coat layers possessed by hard coat films have particularly excellent heat resistance. It is also required to have The hard coat layer in the hard coat film using the above-mentioned UV acrylic monomer can not be said as a sufficient thing also from such a heat resistant viewpoint.

Therefore, an object of the present invention is to provide a polyorganosilsesquioxane having high surface hardness and heat resistance and capable of forming a cured product having excellent flexibility and processability by curing.
Another object of the present invention is to provide a hard coat film having flexibility and being able to be manufactured and processed by a roll-to-roll method while maintaining high surface hardness and heat resistance.
Furthermore, another object of the present invention is to provide the above-mentioned hard coat film which can be further punched.
Furthermore, the other object of the present invention is an adhesive composition (adhesive) capable of forming a cured product (adhesive) having high heat resistance and flexibility, and an adhesive sheet and laminate using the same To provide.

  The present inventors have a silsesquioxane structural unit (unit structure) containing an epoxy group, a ratio of a specific structure (a ratio of T3 body to a T2 body, a ratio of silsesquioxane structural units containing an epoxy group) According to the polyorganosilsesquioxane in which the number average molecular weight and the degree of molecular weight dispersion are controlled in a particular range, by curing the curable composition containing the polyorganosilsesquioxane. It has been found that a cured product having high surface hardness and heat resistance and excellent in flexibility and processability can be formed. Furthermore, the present inventors have found that a hard coat film having a hard coat layer formed from the above hard coat solution containing polyorganosilsesquioxane has flexibility while maintaining high surface hardness and heat resistance. It has been found that it is a hard coat film that can be manufactured and processed by a roll-to-roll method. Furthermore, the present inventors have found that a curable composition containing the above polyorganosilsesquioxane can form a cured product (adhesive) excellent in high heat resistance and flexibility (adhesive agent) It has been found that it can be preferably used as The present invention has been completed based on these findings.

That is, the present invention provides the following formula (1)
[In Formula (1), R ¹ represents a group containing an epoxy group. ]
And a structural unit represented by formula (I) below
[In formula (I), R ^a represents a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group And a substituted or unsubstituted alkenyl group or a hydrogen atom. ]
And a structural unit represented by the following formula (II)
[In formula (II), R ^b is a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group And a substituted or unsubstituted alkenyl group or a hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The molar ratio of the structural units represented by [structural unit represented by formula (I) / structural unit represented by formula (II)] is 5 or more, and the above with respect to the total amount (100 mol%) of the siloxane structural units The structural unit represented by Formula (1) and the following Formula (4)
[In Formula (4), R ¹ is the same as in Formula (1). R ^c is the same as in formula (II). ]
The ratio of the structural unit represented by is 55 to 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion degree (weight average molecular weight / number average molecular weight) is 1.0 to 3.0. Provide a polyorgano silsesquioxane.

Furthermore, the following formula (2)
[In Formula (2), R ² represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group Is an alkenyl group of ]
The above polyorganosilsesquioxane having a constitutional unit represented by

Furthermore, the above R ¹ is represented by the following formula (1a)
[In Formula (1a), R ^1a represents a linear or branched alkylene group. ]
A group represented by the following formula (1b)
[In Formula (1b), R ^1b represents a linear or branched alkylene group. ]
A group represented by the following formula (1c)
[In Formula (1c), R ^1c represents a linear or branched alkylene group. ]
Or a group represented by the following formula (1d)
[In Formula (1d), R ^1d represents a linear or branched alkylene group. ]
The aforementioned polyorganosilsesquioxane which is a group represented by

Furthermore, the above polyorganosilsesquioxane is provided, wherein R ² is a substituted or unsubstituted aryl group.

  The present invention also provides a curable composition comprising the above polyorganosilsesquioxane.

  Furthermore, the above-mentioned curable composition containing a curing catalyst is provided.

  Further, the present invention provides the curable composition, wherein the curing catalyst is a cationic photopolymerization initiator.

  Furthermore, the above curable composition is provided, wherein the curing catalyst is a thermal cationic polymerization initiator.

  Furthermore, the above-mentioned curable composition containing a vinyl ether compound is provided.

  Furthermore, the above-mentioned curable composition containing a vinyl ether compound having a hydroxyl group in the molecule is provided.

  Furthermore, the above-mentioned curable composition which is a curable composition for hard-coat layer formation is provided.

  Furthermore, the above-mentioned curable composition which is a composition for adhesives is provided.

  The present invention also provides a cured product obtained by curing the above-mentioned curable composition.

  Moreover, the present invention is a hard coat film having a substrate and a hard coat layer formed on at least one surface of the substrate, wherein the hard coat layer is a cured product of the curable composition. Provided is a hard coat film characterized by being a layer.

  Furthermore, the hard coat film as described above, wherein the thickness of the hard coat layer is 1 to 200 μm, is provided.

  Furthermore, the above-mentioned hard coat film which can be manufactured by a roll to roll method is provided.

  Furthermore, the above hard coat film having a surface protective film on the surface of the hard coat layer is provided.

  In the present invention, the curable composition is applied to at least one surface of a step A of unwinding a roll-wound base material and the fed-out base material, and then the curable composition is cured. A step B of forming a hard coat layer by the following step, and a step C of winding the obtained hard coat film again on a roll, wherein the steps A to C are carried out continuously. Provide a manufacturing method.

The present invention is also an adhesive sheet comprising a substrate and an adhesive layer on the substrate,
The present invention provides an adhesive sheet characterized in that the adhesive layer is a layer of the curable composition described above.

The present invention is also a laminate comprising three or more layers,
Having two adhesive layers and an adhesive layer between the adhesive layers,
The invention provides a laminate characterized in that the adhesive layer is a layer of a cured product of the curable composition.

  Since the polyorganosilsesquioxane of the present invention has the above constitution, it has high surface hardness and heat resistance by curing a curable composition containing the polyorganosilsesquioxane as an essential component. It is possible to form a cured product having excellent properties and processability. Moreover, since the hard coat film of this invention has the said structure, it has flexibility, maintaining high surface hardness and heat resistance, and manufacture and a process by roll to roll are possible. For this reason, the hard coat film of the present invention is excellent in both quality and cost. Furthermore, the curable composition containing the polyorganosilsesquioxane of the present invention as an essential component is an adhesive composition (adhesive) capable of forming a cured product (adhesive) excellent in high heat resistance and flexibility. It can also be preferably used. An adhesive sheet and a laminate can be obtained by using the adhesive composition.

It is a microscope picture (magnification: 100 times) of the end in the hard coat film after punching processing obtained in Example 20.

[Polyorganosilsesquioxane]
The polyorganosilsesquioxane (silsesquioxane) of the present invention has a constitutional unit represented by the following formula (1); a constitutional unit represented by the following formula (I) (referred to as “T3 body” Molar ratio of a structural unit represented by the following formula (II) (which may be referred to as “T2 form”) [a structural unit represented by the formula (I) / a formula (II) Structural unit; may be described as “T3 body / T2 body” is 5 or more; the structural unit represented by the following formula (1) with respect to the total amount (100 mol%) of the siloxane structural unit and the formula described later The ratio (total amount) of the constituent units represented by (4) is 55 to 100 mol%; the number average molecular weight is 1000 to 3000, the molecular weight dispersion degree [weight average molecular weight / number average molecular weight] is 1.0 to 3. It is characterized by being 0.

The structural unit represented by the said Formula (1) is a silsesquioxane structural unit (what is called T unit) generally represented by [RSiO3 _{/ 2} ]. In addition, R in the said Formula shows a hydrogen atom or monovalent organic group, and is the same also in the following. The structural unit represented by the above formula (1) is formed by hydrolysis and condensation reaction of the corresponding hydrolysable trifunctional silane compound (specifically, for example, a compound represented by the formula (a) described later) Be done.

R ¹ in the formula (1) represents a group containing an epoxy group (a monovalent group). That is, the polyorganosilsesquioxane of the present invention is a cationically curable compound (cationically polymerizable 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 in view of the curability of the curable composition and the surface hardness and heat resistance of the cured product, the following formula The group represented by (1a), the group represented by the following formula (1b), the group represented by the following formula (1c), the group represented by the following formula (1d) are preferable, and more preferably the following formula It is a group represented by 1a), a group represented by the following formula (1c), more preferably a group represented by the following formula (1a).

In the above formula (1a), R ^1a 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. Among them, as R ^1a , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable from the viewpoint of surface hardness and curability of a cured product, and more preferably Ethylene, trimethylene and propylene are preferable, and ethylene and trimethylene are more preferable.

In the above formula (1b), R ^1b represents a linear or branched alkylene group, the same groups as R ^1a is exemplified. Among them, as R ^1b , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable from the viewpoint of surface hardness and curability of a cured product, and more preferably Ethylene, trimethylene and propylene are preferable, and ethylene and trimethylene are more preferable.

In the above formula (1c), R ^1c represents a linear or branched alkylene group, the same groups as R ^1a is exemplified. Among them, as R ^1c , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable in view of surface hardness and curability of a cured product, and more preferably Ethylene, trimethylene and propylene are preferable, and ethylene and trimethylene are more preferable.

In the above formula (1d), R ^1d represents a linear or branched alkylene group, the same groups as R ^1a is exemplified. Among them, as R ^1d , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable from the viewpoint of surface hardness and curability of a cured product, and more preferably Ethylene, trimethylene and propylene are preferable, and ethylene and trimethylene are more preferable.

In particular, R ^{1 in the} formula (1) is a group represented by the above formula (1a), and a group in which R ^1a is an ethylene group [in particular, 2- (3 ′, 4′-epoxycyclohexyl) Ethyl group] is preferable.

  The polyorgano silsesquioxane of the present invention may have only one structural unit represented by the above formula (1), or two or more structural units represented by the above formula (1). You may have.

The polyorgano silsesquioxane of the present invention has a structure represented by the following formula (2) as the silsesquioxane constituent unit [RSiO _3/2 ], in addition to the constituent unit represented by the above formula (1) It may have a unit.

The structural unit represented by the said Formula (2) is a silsesquioxane structural unit (T unit) generally represented by [RSiO3 _{/ 2} ]. That is, the structural unit represented by the above formula (2) is a hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the formula (b) described later) It is formed by

R ² in the above formula (2) is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group Is an alkenyl group of As said aryl group, a phenyl group, a tolyl group, a naphthyl group etc. are mentioned, for example. As said aralkyl group, a benzyl group, a phenethyl group etc. are mentioned, for example. As said cycloalkyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group etc. are mentioned, for example. Examples of the alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group and isopentyl group. Groups are mentioned. As said alkenyl group, linear or branched alkenyl groups, such as a vinyl group, an allyl group, an isopropenyl group, are mentioned, for example.

  As the above-mentioned substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group and substituted alkenyl group, a hydrogen atom or a main chain bone in each of the above-mentioned aryl group, aralkyl group, cycloalkyl group, alkyl group and alkenyl group From the group consisting of an ether group, an ester group, a carbonyl group, a siloxane group, a halogen atom (such as fluorine atom), an acryl group, a methacryl group, a mercapto group, an amino group, and a hydroxy group (hydroxy group) The group substituted by the selected at least 1 sort (s) is mentioned.

Among them, R ² is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, still more preferably a phenyl group is there.

  The proportions of the above-mentioned silsesquioxane constitutional units (the constitutional unit represented by the formula (1), the constitutional unit represented by the formula (2)) in the polyorganosilsesquioxane of the present invention are these constitutional units It is possible to appropriately adjust the composition of the raw material (hydrolyzable trifunctional silane) for forming the

The polyorgano silsesquioxane of the present invention is a structural unit represented by the above formula (1) in addition to the constitutional unit represented by the above formula (1) and the structural unit represented by the formula (2) And silsesquioxane structural units other than the structural unit represented by the formula (2) [RSiO _3/2 ], structural units represented by [R ₃ SiO _1/2 ] (so-called M units), [R ₂ SiO] And at least one siloxane structural unit selected from the group consisting of structural units (so-called Q units) expressed by [SiO ₂ ] and structural units (so-called D units) . In addition, as a silsesquioxane structural unit other than the structural unit represented by said Formula (1), and the structural unit represented by Formula (2), the structural unit etc. which are represented by following formula (3) are It can be mentioned.

  Ratio of structural unit (T3 form) represented by the above formula (I) to structural unit (T2 form) represented by the above formula (II) in the polyorganosilsesquioxane of the present invention [T3 body / T2 body ] Is five or more as mentioned above, Preferably it is 5-18, More preferably, it is 6-16, More preferably, it is 7-14. By setting the ratio [T3 body / T2 body] to 5 or more, the surface hardness and adhesiveness of the cured product and the hard coat layer are remarkably improved.

In addition, when the structural unit represented by said Formula (I) is described in more detail, it will be represented by a following formula (I '). Moreover, when the structural unit represented by the said Formula (II) is described in more detail, it is represented by following formula (II '). Each of the three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I ′) is bonded to another silicon atom (a silicon atom not shown in the formula (I ′)) . On the other hand, the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II ′) are respectively the other silicon atoms (silicon atoms not shown in the formula (II ′)) It is connected. That is, the above T3 body and T2 body are both structural units (T units) formed by hydrolysis and condensation reaction of the corresponding hydrolysable trifunctional silane compound.

R ^a in the above formula (I) (formula (I ') in the R ^a same) and formula (II) in the R ^b (wherein (II') in the R ^b versa), respectively, an epoxy group A substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. Show. Specific examples of R ^a and R ^b include the same as R ¹ in the above formula (1) and R ² in the above formula (2). In addition, R ^a in formula (I) and R ^b in formula (II) are each bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material of the polyorganosilsesquioxane of the present invention It originates in groups (groups other than an alkoxy group and a halogen atom; For example, R < ¹ >, R < ² >, hydrogen atom etc. in below-mentioned Formula (a)-(c)).

R ^c in the above formula (II) (same as R ^c in formula (II ′)) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As a C1-C4 alkyl group, C1-C4 linear or branched alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, an isobutyl group, are mentioned, for example . The alkyl group for R ^c in the formula (II) is generally an alkoxy group in the hydrolyzable silane compound used as a raw material of the polyorganosilsesquioxane of the present invention (for example, X ^{1 to} X ³ described below) Derived from an alkyl group forming an alkoxy group etc.

The ratio [T3 body / T2 body] in the polyorganosilsesquioxane of the present invention can be determined, for example, by ²⁹ Si-NMR spectrum measurement. ^{In the 29} Si-NMR spectrum, the silicon atom in the constituent unit (T3 form) represented by the above formula (I) and the silicon atom in the constituent unit (T2 form) represented by the above formula (II) are at different positions Since the signal (peak) is shown in (chemical shift), the ratio [T3 body / T2 body] can be obtained by calculating the integral ratio of each of these peaks. Specifically, for example, the polyorganosilsesquioxane of the present invention has a constitutional unit represented by the above formula (1) and R ¹ is a 2- (3 ', 4'-epoxycyclohexyl) ethyl group. In this case, the signal of the silicon atom in the structure (T3 form) represented by the above formula (I) appears at -64 to -70 ppm, and the silicon atom in the structure (T2 form) represented by the above formula (II) The signal appears at -54 to -60 ppm. Therefore, in this case, the ratio [T3 body / T2 body] can be determined by calculating the integral ratio of the −64 to −70 ppm signal (T3 body) and the −54 to −60 ppm signal (T2 body). it can.

The ²⁹ Si-NMR spectrum of the polyorganosilsesquioxane of the present invention 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 fact that the above ratio [T3 body / T2 body] of the polyorganosilsesquioxane of the present invention is 5 or more means that, in the polyorganosilsesquioxane of the present invention, a T2 body of a certain amount or more exists relative to the T3 body. Means to As such a T2 body, for example, a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), and the like can be mentioned. R ² in R ¹ and the following formula (5) in the following equation (4) is the same as R ² in R ¹ and the formula in the formula (1) (2). R ^c in the following formulas (4) to (6) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, as R ^c in the formula (II).

In general, completely cage silsesquioxane is a polyorganosilsesquioxane constituted only by T3 form, and T2 form does not exist in the molecule. That is, the ratio [T3 body / T2 body] is 5 or more, the number average molecular weight is 1000 to 3000, the molecular weight dispersion degree is 1.0 to 3.0, and further in the FT-IR spectrum as described later. It is suggested that the polyorganosilsesquioxane of the present invention having one intrinsic absorption peak at around 1100 cm ^-1 has an incomplete cage silsesquioxane structure.

The fact that the polyorganosilsesquioxane of the present invention has a cage-type (incomplete cage type) silsesquioxane structure is that the polyorganosilsesquioxane of the present invention has an FT-IR spectrum around 1050 cm ^-1 and 1150 cm respectively in the vicinity of ^-1 it does not have a specific absorption peak is confirmed by the fact that with a single specific absorption peak in the vicinity of 1100 cm ^-1 [ref: R. H. Raney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. On the other hand, when it has an intrinsic absorption peak near 1050 cm ^-1 and 1150 cm ^-1 respectively in the FT-IR spectrum, it is generally identified as having a ladder type silsesquioxane structure. The FT-IR spectrum of the polyorganosilsesquioxane of the present invention can be measured, for example, by the following apparatus and conditions.
Measuring device: Brand name "FT-720" (manufactured by Horiba, Ltd.)
Measurement method: Transmission method Resolution: 4 cm ^-1
Measurement wave number range: 400 to 4000 cm ^-1
Accumulated number of times: 16 times

  The total amount of siloxane constitutional units in the polyorganosilsesquioxane of the present invention [all siloxane constitutional units; M units, D units, T units, and total amount of Q units] (100 mol%) is shown in the above-mentioned formula (1) The proportion (total amount) of the constituent units represented by the formula (4) and the constituent unit represented by the above formula (4) is 55 to 100 mol%, preferably 65 to 100 mol%, more preferably 80 to 99, as described above. It is mol%. By setting the ratio to 55 mol% or more, the curability of the curable composition is improved, and the surface hardness and adhesiveness of the cured product become extremely high. In addition, the ratio of each siloxane structural unit in the polyorgano silsesquioxane of this invention can be calculated, for example by the composition of a raw material, NMR spectrum measurement, etc.

  The total amount of siloxane constitutional units in the polyorganosilsesquioxane of the present invention [all siloxane constitutional units; M units, D units, T units, and total amount of Q units] (100 mol%) is shown in the above-mentioned formula (2) No particular limitation is imposed on the proportion (total amount) of the constituent unit represented by the formula (5) and the constituent unit represented by the above formula (5), but 0 to 70 mol% is preferable, more preferably 0 to 60 mol%, still more preferably 0 It is 40 mol%, particularly preferably 1 to 15 mol%. Since the ratio of the structural unit represented by Formula (1) and the structural unit represented by Formula (4) can be increased relatively by setting the ratio to 70 mol% or less, the curable composition There is a tendency that the curability of the resin improves and the surface hardness and adhesiveness of the cured product become higher. On the other hand, when the ratio is 1 mol% or more, the gas barrier properties of the cured product tend to be improved.

  The total amount of siloxane constitutional units in the polyorganosilsesquioxane of the present invention [all siloxane constitutional units; M units, D units, T units, and total amount of Q units] (100 mol%) is shown in the above-mentioned formula (1) The ratio (total amount) of the constitutional unit to be used, the constitutional unit represented by the above formula (2), the constitutional unit represented by the above formula (4), and the constitutional unit represented by the above formula (5) is particularly limited Although not preferred, it is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%. By setting the ratio to 60 mol% or more, the surface hardness and adhesion of the cured product tend to be higher.

  The number average molecular weight (Mn) in terms of standard polystyrene equivalent by gel permeation chromatography of the polyorganosilsesquioxane of the present invention is 1000 to 3000, preferably 1000 to 2800, and more preferably 1100 to 3000, as described above. 2600. By making the number average molecular weight 1000 or more, the heat resistance, the abrasion resistance and the adhesion of the cured product are further improved. On the other hand, by setting the number average molecular weight to 3000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product is further improved.

  The standard polystyrene equivalent molecular weight dispersion degree (Mw / Mn) by gel permeation chromatography of the polyorganosilsesquioxane of the present invention is, as described above, 1.0 to 3.0, preferably 1.1. It is -2.0, more preferably 1.2-1.9. By setting the molecular weight dispersion degree to 3.0 or less, the surface hardness and adhesion of the cured product become higher. On the other hand, when the degree of dispersion of molecular weight is 1.1 or more, it tends to be liquid, and the handleability tends to be improved.

In addition, the number average molecular weight of the polyorgano 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

The 5% weight loss temperature (T _d5 ) of the polyorganosilsesquioxane of the present invention under an air atmosphere is not particularly limited, but is preferably 330 ° C. or more (eg, 330 to 450 ° C.), more preferably 340 ° C. or more More preferably, it is 350 ° C. or higher. When the 5% weight loss temperature is 330 ° C. or more, the heat resistance of the cured product tends to be further improved. In particular, the polyorganosilsesquioxane of the present invention has a ratio [T3 body / T2 body] of 5 or more, a number average molecular weight of 1000 to 3000, and a molecular weight dispersion degree of 1.0 to 3.0. The 5% weight loss temperature is controlled to 330 ° C. or higher by having one unique peak around 1100 cm ⁻¹ in the FT-IR spectrum. The 5% weight loss temperature is the temperature at which 5% of the weight before heating decreases when heated at a constant temperature rising rate, and serves as an indicator of heat resistance. The 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under an air atmosphere at a temperature rising rate of 5 ° C./minute.

  The polyorganosilsesquioxane of the present invention can be produced by a known or commonly used method for producing polysiloxane, and is not particularly limited. For example, one or two or more hydrolysable silane compounds can be hydrolyzed and It can be produced by a method of condensation. However, as the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (compound represented by the following formula (a)) for forming a constitutional unit represented by the above-mentioned formula (1) is essential. It should be used as a hydrolyzable silane compound.

More specifically, for example, a compound represented by the following formula (a) which is a hydrolyzable silane compound for forming a silsesquioxane structural unit (T unit) in the polyorganosilsesquioxane of the present invention If necessary, the polyorganosilsesquioxane of the present invention can be produced by a method of hydrolyzing and condensing a compound represented by the following formula (b) and a compound represented by the following formula (c) .

The compound represented by the said Formula (a) is a compound which forms the structural unit represented by Formula (1) in polyorgano silsesquioxane of this invention. R ¹ in the formula (a), like that of R ¹ in the formula (1), a group containing an epoxy group. That is, as R ¹ in the formula (a), a group represented by the above formula (1a), a group represented by the above formula (1b), a group represented by the above formula (1c), the above formula (1d) Is more preferably a group represented by the above formula (1a), a group represented by the above formula (1c), still more preferably a group represented by the above formula (1a), particularly preferably Is a group represented by the above formula (1a), and is a group in which R ^1a is an ethylene group (in particular, 2- (3 ', 4'-epoxycyclohexyl) ethyl group).

X ¹ in the above formula (a) represents an alkoxy group or a halogen atom. The alkoxy group in X ^1, for example, a methoxy group, an ethoxy group, a propoxy group, isopropyloxy group, a butoxy group, an alkoxy group having 1 to 4 carbon atoms such as isobutyl group and the like. As the halogen atom in X ^1, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, X ¹ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ^{1 s} may be identical to or different from each other.

The compound represented by the said Formula (b) is a compound which forms the structural unit represented by Formula (2) in polyorgano silsesquioxane of this invention. R ² in formula (b), like the R ² in the formula (2), a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted Or an alkyl or substituted or unsubstituted alkenyl group. That is, R ² in the formula (b) is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, More preferably, it is a phenyl group.

X ² in the above formula (b) represents an alkoxy group or a halogen atom. Specific examples of X ² include those exemplified as X ¹ . Among them, X ² is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. In addition, three X ² may be identical to or different from each other.

The compound represented by the said Formula (c) is a compound which forms the structural unit represented by Formula (3) in polyorgano silsesquioxane of this invention. X ³ in the above formula (c) represents an alkoxy group or a halogen atom. Specific examples of X ³ include those exemplified as X ¹ . Among them, X ³ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. In addition, three X ³ may be identical to or different from each other.

  As said hydrolysable silane compound, you may use together hydrolysable silane compounds other than the compound represented by said Formula (a)-(c). For example, hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (a) to (c), hydrolyzable monofunctional silane compounds forming M units, hydrolyzable bifunctional silanes forming D units The compound, the hydrolysable tetrafunctional silane compound which forms Q unit, etc. are mentioned.

  The amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane of the present invention. For example, the amount of the compound represented by the above formula (a) is not particularly limited, but is preferably 55 to 100 mol%, more preferably the total amount (100 mol%) of the hydrolyzable silane compound to be used. Is 65 to 100 mol%, more preferably 80 to 99 mol%.

  The amount of the compound represented by the above formula (b) is not particularly limited, but is preferably 0 to 70 mol%, more preferably the total amount (100 mol%) of the hydrolyzable silane compound to be used. Is preferably 0 to 60 mol%, more preferably 0 to 40 mol%, particularly preferably 1 to 15 mol%.

  Furthermore, the ratio (ratio of the total amount) of the compound represented by the formula (a) to the compound represented by the formula (b) with respect to the total amount (100 mol%) of the hydrolyzable silane compound used is not particularly limited. 60-100 mol% is preferable, More preferably, it is 70-100 mol%, More preferably, it is 80-100 mol%.

  Moreover, when using 2 or more types together as said hydrolysable silane compound, a hydrolysis and condensation reaction of these hydrolysable silane compounds can also be performed simultaneously, and can also be performed sequentially. 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 can be carried out in the presence or absence of a solvent. Above all, it is preferable to carry out 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. Among the above solvents, ketones and ethers are preferable. In addition, a solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The amount of the solvent used is not particularly limited, and can be appropriately adjusted according to the desired reaction time and the like within the range of 0 to 2000 parts by weight with respect to 100 parts by weight of the total amount of the hydrolysable 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. The catalyst may be an acid catalyst or an alkali catalyst. 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 and sodium hydrogen carbonate And hydrogen carbonates of alkali metals such as cesium hydrogen carbonate; organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate and cesium acetate (for example, acetates); organic acids of alkaline earth metals such as magnesium acetate Salts (eg, acetate); lithium methoxide, sodium methoxy Alkoxides of alkali metals such as sodium ethoxide, 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] Undec-7-ene, amines such as 1,5-diazabicyclo [4.3.0] non-5-ene (tertiary amines etc.); pyridine, 2,2'-bipyridyl, 1,10 -Nitrogen-containing aromatic heterocyclic compounds such as phenanthroline and the like can be mentioned. In addition, a catalyst can also be used individually by 1 type, and can also be used in combination of 2 or more type. 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 can be appropriately adjusted within the range of 0.002 to 0.200 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound.

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

  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.

  Especially as reaction conditions at the time of performing the hydrolysis and condensation reaction of the above-mentioned hydrolysable silane compound, the reaction that the above-mentioned ratio [T3 body / T2 body] in the polyorgano silsesquioxane of the present invention becomes 5 or more It is important to select the conditions. Although the reaction temperature of the said hydrolysis and condensation reaction is not specifically limited, 40-100 degreeC is preferable, More preferably, it is 45-80 degreeC. By controlling the reaction temperature within the above range, the ratio [T3 body / T2 body] tends to be able to be controlled more efficiently to 5 or more. 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 1.5 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.

  The polyorgano silsesquioxane of this invention is obtained by the hydrolysis and condensation reaction of the said hydrolysable silane compound. After the completion of the above-mentioned hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress the ring opening of the epoxy group. In addition, for example, separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and the like, and the polyorgano silsesquioxanes of the present invention are combined. You may separate and refine by separation means etc.

  Since the polyorganosilsesquioxane of the present invention has the above-mentioned constitution, it has high surface hardness and heat resistance by curing a curable composition containing the polyorganosilsesquioxane as an essential component. It is possible to form a cured product excellent in flexibility and processability. In addition, a cured product with excellent adhesion can be formed.

[Curable composition]
The curable composition of the present invention is a curable composition (curable resin composition) containing the above-described polyorganosilsesquioxane of the present invention as an essential component. As described later, the curable composition of the present invention may further contain other components such as a curing catalyst (in particular, a cationic photopolymerization initiator), a surface conditioner, or a surface modifier.

  In the curable composition of the present invention, the polyorganosilsesquioxanes of the present invention can be used alone or in combination of two or more.

  The content (blending amount) of the polyorganosilsesquioxane of the present invention in the curable composition of the present invention is not particularly limited, but it is 70 with respect to the total amount (100% by weight) of the curable composition excluding the solvent. % By weight or more and less than 100% by weight is preferable, more preferably 80 to 99.8% by weight, still more preferably 90 to 99.5% by weight. By setting the content of the polyorganosilsesquioxane of the present invention to 70% by weight or more, the surface hardness and adhesion of the cured product tend to be further improved. On the other hand, when the content of the polyorganosilsesquioxane of the present invention is less than 100% by weight, a curing catalyst can be contained, whereby the curing of the curable composition can proceed more efficiently. It tends to be possible.

  The proportion of the polyorganosilsesquioxane of the present invention to the total amount (100% by weight) of the cationically curable compound contained in the curable composition of the present invention is not particularly limited, but 70 to 100% by weight is preferable, more preferably Is 75 to 98% by weight, more preferably 80 to 95% by weight. By setting the content of the polyorganosilsesquioxane of the present invention to 70% by weight or more, the surface hardness and adhesion of the cured product tend to be further improved.

  The curable composition of the present invention preferably further comprises a curing catalyst. Among them, it is particularly preferable to include a photo cationic polymerization initiator as a curing catalyst in that the curing time until tack-free can be shortened.

  The curing catalyst is a compound capable of initiating or accelerating the cationic polymerization reaction of the cationically curable compound such as polyorganosilsesquioxane of the present invention. Although it does not specifically limit as said curing catalyst, For example, polymerization initiators, such as a photo cationic polymerization initiator (photo-acid generator), a thermal cationic polymerization initiator (thermal acid generator), are mentioned.

  As the photocationic polymerization initiator, known or commonly used photocationic polymerization initiators can be used. For example, sulfonium salt (salt of sulfonium ion and anion), iodonium salt (salt of iodonium ion and anion) Selenium salts (salts of selenium ions and anions), ammonium salts (salts of ammonium ions and anions), phosphonium salts (salts of phosphonium ions and anions), salts of transition metal complex ions and anions, etc. . These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the sulfonium salt include, for example, trade name “HS-1PC” (manufactured by San-Apro Co., Ltd.), trade name “LW-S1” (manufactured by San-Apro Co., Ltd.), triphenylsulfonium salt, tri-p-tolylsulfonium salt Tri-o-tolyl sulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyl diphenyl sulfonium salt, 2-naphthyl diphenyl sulfonium salt, tris (4-fluorophenyl) sulfonium salt, tri-1-naphthyl sulfonium salt , Tri-2-naphthylsulfonium salts, tris (4-hydroxyphenyl) sulfonium salts, diphenyl [4- (phenylthio) phenyl] sulfonium salts, 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium salts, etc. Reel sulfonium salt; diphenyl Diarylsulfonium salts such as phenacyl sulfonium salt, diphenyl 4-nitrophenacyl sulfonium salt, diphenyl benzyl sulfonium salt, diphenyl methyl sulfonium salt, etc .; phenyl methyl benzyl sulfonium salt, 4-hydroxyphenyl methyl benzyl sulfonium salt, 4-methoxyphenyl methyl benzyl Examples include monoarylsulfonium salts such as sulfonium salts; and trialkylsulfonium salts such as dimethylphenacylsulfonium salts, phenacyltetrahydrothiophenium salts, and dimethylbenzylsulfonium salts.

  As said diphenyl [4- (phenylthio) phenyl] sulfonium salt, the brand name "CPI-101A" (The Sanapro Co., Ltd. product, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate 50% propylene carbonate solution is made, for example) Commercial products such as trade name "CPI-100P" (manufactured by San-Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate 50% propylene carbonate solution) can be used. Moreover, as said triaryl sulfonium salt, you may use commercial products, such as brand name "K1-S" (San-Apro Co., Ltd. product, non-antimony type triaryl sulfonium salt) etc., for example.

  Examples of the above-mentioned iodonium salts include “UV9380C” (manufactured by Momentive Performance Materials Japan LLC, bis (4-dodecylphenyl) iodonium = 45% solution of hexafluoroantimonate alkyl glycidyl ether), trade name “ RHODORSIL PHOTOINITIATOR 2074 (manufactured by Rhodia Japan Ltd., tetrakis (pentafluorophenyl) borate = [(1-methylethyl) phenyl] (methylphenyl) iodonium), trade name “WPI-124” (Wako Pure Chemical Industries, Ltd. Co., Ltd., diphenyliodonium salt, di-p-tolylliodonium salt, bis (4-dodecylphenyl) iodonium salt, bis (4-methoxyphenyl) iodonium salt and the like.

  Examples of the selenium salts include triarylseleniums such as triphenylselenium salts, tri-p-tolylselenium salts, tri-o-tolylselenium salts, tris (4-methoxyphenyl) selenium salts, and 1-naphthyldiphenylselenium salts. Salts; diarylselenium salts such as diphenylphenacylselenium salts, diphenylbenzylselenium salts, diphenylmethylselenium salts; monoarylselenium salts such as phenylmethylbenzylselenium salts; trialkylselenium salts such as dimethylphenacylselenium salts .

  Examples of the ammonium salt include tetramethyl ammonium salt, ethyl trimethyl ammonium salt, diethyl dimethyl ammonium salt, triethyl methyl ammonium salt, tetraethyl ammonium salt, trimethyl n-propyl ammonium salt, and tetra methyl n-butyl ammonium salt. Alkyl ammonium salts; pyrrolidinium salts such as N, N-dimethyl pyrrolidinium salts, N-ethyl-N-methyl pyrrolidinium salts, etc .; N, N'-dimethyl imidazolinium salts, N, N'-diethyl imidazolinium salts, etc. Imidazolinium salts of N, N'-dimethyltetrahydropyrimidium salts, tetrahydropyrimidium salts such as N, N'-diethyltetrahydropyrimidium salts; N, N-dimethylmorpholinium salts, N, N -Diethylmorpholinium salt Morpholinium salts such as N, N-dimethylpiperidinium salts, piperidinium salts such as N, N-diethylpiperidinium salts, etc .; N-methyl pyridinium salts, pyridinium salts such as N-ethyl pyridinium salts; N, N'- Imidazolium salts such as dimethyl imidazolium salts; quinolium salts such as N-methyl quinolium salts; isoquinolium salts such as N-methyl isoquinolium salts; thiazonium salts such as benzyl benzothiazonium salts; benzyl acridium salts Acridium salts and the like.

  Examples of the phosphonium salts include tetraarylphosphonium salts such as tetraphenylphosphonium salts, tetra-p-tolylphosphonium salts, tetrakis (2-methoxyphenyl) phosphonium salts and the like; triarylphosphonium salts such as triphenylbenzylphosphonium salts and the like; triethyl Examples thereof include benzyl phosphonium salts, tributyl benzyl phosphonium salts, tetraethyl phosphonium salts, tetrabutyl phosphonium salts, and tetraalkyl phosphonium salts such as triethyl phenacyl phosphonium salts.

Examples of salts of the above transition metal complex ions include salts of chromium complex cations such as (η5-cyclopentadienyl) (η6-toluene) Cr ⁺ , (η5-cyclopentadienyl) (η6-xylene) Cr ^{+ and the} like. And salts of iron complex cations such as (5−5-cyclopentadienyl) (6−6-toluene) Fe ⁺ , (η5-cyclopentadienyl) (η6-xylene) Fe ^{+, and the} like.

Examples of the anion constituting the above-mentioned salt include SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , sulfonate anion (trifluoromethane sulfonate anion, pentafluoroethane sulfonate anion, nonafluorobutane sulfonate anion, methane sulfonate anion, benzene sulfonic acid anion, p- toluenesulfonate anion, _{etc.), (CF 3 SO 2)} 3 C -, (CF 3 SO 2) 2 N -, perhalogenated acid ion, a halogenated sulfonic acid ion, carbonate ion, aluminate Ions, hexafluorobisamic acid ion, carboxylic acid ion, aryl borate ion, thiocyanate ion, nitrate ion and the like can be mentioned.

  Examples of the thermal cationic polymerization initiator include arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes.

  Examples of the arylsulfonium salt include hexafluoroantimonate salts and the like. In the curable composition of the present invention, for example, trade names "SP-66", "SP-77" (all, manufactured by ADEKA Co., Ltd.); trade names "Sun-Aid SI-60L", "San-Aid SI-80L" Commercial products such as “San Aid SI-100L” and “San Aid SI-150L” (all manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. Examples of the aluminum chelate include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate) and the like. Moreover, as said boron trifluoride amine complex, a boron trifluoride monoethylamine complex, a boron trifluoride imidazole complex, a boron trifluoride piperidine complex etc. are mentioned, for example.

  In the curable composition of the present invention, one kind of curing catalyst may be used alone, or two or more kinds may be used in combination.

  The content (blending amount) of the curing catalyst in the curable composition of the present invention is not particularly limited, but 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the polyorganosilsesquioxane of the present invention Is more preferably 0.05 to 3.0 parts by weight, and still more preferably 0.1 to 1.0 parts by weight (e.g. 0.3 to 1.0 parts by weight). By setting the content of the curing catalyst to 0.01 parts by weight or more, the curing reaction can be efficiently advanced sufficiently, and the surface hardness and adhesiveness of the cured product tend to be further improved. On the other hand, when the content of the curing catalyst is 3.0 parts by weight or less, the storability of the curable composition tends to be further improved, and the coloring of the cured product tends to be suppressed.

  The curable composition of the present invention may further contain a cationic curable compound other than the polyorganosilsesquioxane of the present invention (sometimes referred to as "other cationic curable compound"). As other cationically curable compounds, known or commonly used cationically curable compounds can be used and are not particularly limited. For example, epoxy compounds other than the polyorganosilsesquioxane of the present invention ("Other epoxy compounds And the like), an oxetane compound, a vinyl ether compound and the like. In the curable composition of the present invention, other cationically curable compounds can be used alone or in combination of two or more.

  As the above-mentioned other epoxy compounds, known or common compounds having one or more epoxy groups (oxirane ring) in the molecule can be used, and although not particularly limited, for example, alicyclic epoxy compounds (alicyclic Epoxy resin), aromatic epoxy compound (aromatic epoxy resin), aliphatic epoxy compound (aliphatic epoxy resin), etc. may be mentioned.

  Examples of the above-mentioned alicyclic epoxy compounds 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, (1) A compound having an epoxy group (referred to as "alicyclic epoxy group") composed of two adjacent carbon atoms constituting an alicyclic ring and an oxygen atom; (2) the epoxy group is directly bonded to the alicyclic ring by a single bond (3) compounds having an alicyclic and glycidyl ether group in the molecule (glycidyl ether type epoxy compounds) and the like.

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.

  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. Examples thereof include divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.

  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.

As a typical example of the alicyclic epoxy compound represented by said Formula (i), 3,4,3 ', 4'- diepoxy bi cyclohexane, following formula (i-1)-(i-10) And the like. In the following formulas (i-5) and (i-7), l and m each represent an integer of 1 to 30. R 'in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched chain having 1 to 3 carbon atoms such as methylene, ethylene, propylene or isopropylene. Like alkylene groups are preferred. N1 to n6 in the following formulas (i-9) and (i-10) each represent an integer of 1 to 30. Moreover, as an alicyclic epoxy compound represented by said Formula (i), the other, for example, 2, 2-bis (3, 4- epoxycyclohexyl) propane, 1, 2- bis (3, 4- epoxycyclohexyl, And ethane), 2,3-bis (3,4-epoxycyclohexyl) oxirane, and bis (3,4-epoxycyclohexylmethyl) ether.

Examples of the compound in which an epoxy group is directly bonded to the (2) alicyclic ring described above by a single bond include a compound represented by the following formula (ii), and the like.

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 each represent a natural number. Examples of the polyhydric alcohol [R ′ (OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (alcohols having 1 to 15 carbon atoms), and the like. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in the respective groups in () (outside parentheses) 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 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 .; Epoxides of (including alkadiene) and the like can be mentioned. 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.

  In the curable composition of the present invention, it is preferable to use a vinyl ether compound in combination with the polyorganosilsesquioxane of the present invention as another cationically curable compound. This tends to further increase the surface hardness of the cured product. In particular, when the curable composition of the present invention is cured by irradiation with active energy rays (in particular, ultraviolet rays), cured products having very high surface hardness are excellent even when the irradiation amount of active energy rays is lowered. There is an advantage that it can be obtained with high productivity (for example, it is not necessary to apply a heat treatment for aging). For this reason, it is possible to further increase the production line speed of the cured product and the hard coat film, and the productivity thereof is further improved.

  In addition, particularly when a vinyl ether compound having one or more hydroxyl groups in the molecule is used as another cationically curable compound, the surface hardness is higher, and further, heat yellowing resistance (yellowing hardly occurs due to heating) It has the advantage that a cured product excellent in the properties) can be obtained. For this reason, a cured product or hard coat film of higher quality and higher durability can be obtained. The number of hydroxyl groups in the molecule of the vinyl ether compound having one or more hydroxyl groups in the molecule is not particularly limited, but is preferably 1 to 4 and more preferably 1 or 2. Specifically, as a vinyl ether compound having one or more hydroxyl groups in the molecule, for example, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy isopropyl Vinylether, 4-hydroxybutylvinylether, 3-hydroxybutylvinylether, 2-hydroxybutylvinylether, 3-hydroxyisobutylvinylether, 2-hydroxyisobutylvinylether, 1-methyl-3-hydroxypropylvinylether, 1-methyl-2-hydroxypropyl Vinyl ether, 1-hydroxymethyl propyl vinyl ether, 4-hydroxy cyclohexyl vinyl ether, 1, 6-hexa Diol monovinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, tripropylene glycol Monovinyl ether, tetra B propylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, oligo propylene glycol monomethyl ether, polypropylene glycol monovinyl ether, pentaerythritol trivinyl ether, dipentaerythritol penta vinyl ether.

  The content (blending amount) of the other cationically curable compound in the curable composition of the present invention is not particularly limited, but the total amount (100% by weight) of the polyorganosilsesquioxane of the present invention and the other cationically curable compound 50% by weight or less (eg, 0 to 50% by weight) is preferable, more preferably 30% by weight or less (eg, 0 to 30% by weight), further preferably 10% by weight based on the total amount of the cationically curable compound % Or less. By setting the content of the other cationically curable compound to 50% by weight or less (particularly 10% by weight or less), the scratch resistance of the cured product tends to be further improved. On the other hand, by setting the content of the other cationically curable compound to 10% by weight or more, desired performance with respect to the curable composition and the cured product (for example, rapid curing and viscosity adjustment for the curable composition, etc.) May be granted.

  The content (blending amount) of the vinyl ether compound (in particular, the vinyl ether compound having one or more hydroxyl groups in the molecule) in the curable composition of the present invention is not particularly limited, but the polyorganosilsesquioxane of the present invention The amount is preferably 0.01 to 10% by weight, more preferably 0.05 to 9% by weight, and still more preferably 1 to 10% by weight, based on the total amount (100% by weight; the total amount of the cation curable compounds) of the other cationically curable compounds. It is 8% by weight. By controlling the content of the vinyl ether compound in the above range, the surface hardness of the cured product becomes higher, and the curing is very high in surface hardness even when the irradiation amount of active energy rays (for example, ultraviolet light) is lowered. There is a tendency for things to be obtained. In particular, by controlling the content of the vinyl ether compound having one or more hydroxyl groups in the molecule within the above range, in addition to the surface hardness of the cured product becoming particularly high, its heat resistant yellowing tends to be further improved. is there.

  The curable composition of the present invention may further contain, as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate Inorganic fillers such as carbon black, silicon carbide, silicon nitride and boron nitride; inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes and organosilazanes; silicone resins, epoxy resins Organic resin fine powder such as fluorocarbon resin; Filler such as conductive metal powder such as silver and copper, curing agent, solvent (organic solvent etc.), stabilizer (antioxidant, ultraviolet absorber, light stabilizer) , Heat stabilizers, heavy metal deactivators etc., flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants etc), flame retardants Agents, reinforcing agents (such as other fillers), nucleating agents, coupling agents (such as silane coupling agents), lubricants, waxes, plasticizers, mold release agents, impact modifiers, hue improvers, clarifying agents, Rheology modifiers (such as flow improvers), processability improvers, colorants (such as dyes and pigments), antistatic agents, dispersants, surface conditioners (such as antifoaming agents, leveling agents, anti-slip agents), surfaces Conventional agents such as modifiers (slip agents, etc.), matting agents, antifoaming agents, foam inhibitors, defoamers, antibacterial agents, preservatives, viscosity modifiers, thickeners, photosensitizers, foaming agents, etc. It may contain an additive. These additives may be used alone or in combination of two or more.

  Although the curable composition of the present invention is not particularly limited, it can be prepared by stirring and mixing the above-mentioned components at room temperature or while heating as needed. In addition, the curable composition of this invention can also be used as a one-component composition which uses what was mixed each component beforehand as it is, for example, two or more components stored separately It can also be used as a composition of a multi-component system (for example, a two-component system) which is used by mixing at a predetermined ratio before use.

  The curable composition of the present invention is not particularly limited, but is preferably liquid at normal temperature (about 25 ° C.). More specifically, the curable composition of the present invention has a viscosity at 25 ° C. of a liquid diluted in a solvent 20% [in particular, a curable composition (solution) in which the proportion of methyl isobutyl ketone is 20% by weight]. The viscosity is preferably 300 to 20,000 mPa · s, more preferably 500 to 10,000 mPa · s, and still more preferably 1,000 to 8,000 mPa · s. By setting the viscosity to 300 mPa · s or more, the heat resistance of the cured product tends to be further improved. On the other hand, by setting the viscosity to 20000 mPa · s or less, preparation and handling of the curable composition become easy, and bubbles tend not to remain in the cured product. 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 5% swing angle, a frequency of 0.1 to 100 (1 / s), and a temperature: Measured under conditions of 25 ° C.

[Cured product]
The curable composition can be cured by advancing the polymerization reaction of a cationic curable compound (such as the polyorganosilsesquioxane of the present invention) in the curable composition of the present invention, and a cured product ("This The cured product of the invention may be referred to as The method of curing can be appropriately selected from known methods, and is not particularly limited, and examples thereof include irradiation with active energy rays and / or a method of heating. 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.

  On the other hand, conditions for curing the curable composition of the present invention by heating are not particularly limited, but for example, 30 to 200 ° C. are preferable, and more preferably 50 to 190 ° C. The curing time can be set appropriately.

  As described above, the curable composition of the present invention can be cured to form a cured product having high surface hardness and heat resistance and excellent in flexibility and processability. Therefore, the curable composition of the present invention is, in particular, a "curable composition for forming a hard coat layer" (a "hard coat solution", a "hard coat agent", etc.) for forming a hard coat layer in a hard coat film. It can be particularly preferably used as sometimes referred to). A hard coat film having a hard coat layer formed from the composition using the curable composition of the present invention as a hard coat layer-forming curable composition is flexible while maintaining high hardness and high heat resistance. It can be manufactured and processed by roll-to-roll.

[Hard coat film]
The hard coat film of the present invention is a film having a substrate and a hard coat layer formed on at least one surface of the substrate, and the above hard coat layer is a curable composition of the present invention (hard It is characterized in that it is a hard coat layer (cured product layer of the curable composition of the present invention) formed by the curable composition for forming a coat layer). In the present specification, the above-mentioned hard coat layer formed of the curable composition of the present invention may be referred to as "the hard coat layer of the present invention".

  The hard coat layer of the present invention in the hard coat film of the present invention may be formed only on one surface (one side) of the above-mentioned substrate, or may be formed on both surfaces (both sides) .

  In addition, the hard coat layer of the present invention in the hard coat film of the present invention may be formed only on a part of the surface of each of the above-mentioned substrates, or may be formed on the entire surface.

  The base material in the hard coat film of the present invention is a base material of a hard coat film, and refers to a portion which constitutes other than the hard coat layer of the present invention. As the above-mentioned substrate, publicly known materials such as plastic substrates, metal substrates, ceramic substrates, semiconductor substrates, glass substrates, paper substrates, wood substrates (wood substrates), substrates whose surfaces are coated surfaces, etc. Conventional substrates can be used without particular limitation. Among them, plastic substrates (substrates made of plastic materials) are preferable.

  The plastic material constituting the plastic substrate is not particularly limited, but, for example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyimides; polycarbonates; polyamides; polyacetals; polyacetals; polyphenylene oxides; polyphenylene sulfides; Sulfone: Polyether ether ketone; Homopolymer of norbornene monomer (addition polymer, ring opening polymer, etc.), copolymer of norbornene monomer and olefin monomer such as copolymer of norbornene and ethylene (addition polymer And cyclic olefin copolymers such as ring-opening polymers), cyclic polyolefins such as derivatives thereof; vinyl polymers (for example, acrylic resins such as polymethyl methacrylate (PMMA); , Polyvinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin etc.); vinylidene polymers (eg polyvinylidene chloride etc); cellulose resins such as triacetyl cellulose (TAC); epoxy resin; phenol resin; Melamine resin; urea resin; maleimide resin; various plastic materials such as silicone. The plastic base may be made of only one type of plastic material, or may be made of two or more types of plastic materials.

  Among them, when it is intended to obtain a hard coat film excellent in transparency as the hard coat film of the present invention as the above-mentioned plastic base material, a substrate excellent in transparency (transparent base material) should be used. And more preferably polyester films (especially, PET, PEN), cyclic polyolefin films, polycarbonate films, TAC films, PMMA films.

  The above-mentioned plastic substrate is, if necessary, an antioxidant, an ultraviolet light absorber, a light stabilizer, a thermal stabilizer, a crystal nucleating agent, a flame retardant, a flame retardant auxiliary, a filler, a plasticizer, an impact modifier Other additives such as a reinforcing agent, a dispersing agent, an antistatic agent, a foaming agent and an antibacterial agent may be included. In addition, an additive can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The plastic substrate may have a single-layer structure or a multi-layer (laminated) structure, and the structure (structure) is not particularly limited. For example, the above plastic substrate is a “plastic film / other layer” in which a layer other than the hard coat layer of the present invention (sometimes referred to as “other layer”) is formed on at least one surface of the plastic film. Alternatively, it may be a plastic substrate having a laminated structure such as “other layer / plastic film / other layer”. As said other layer, hard-coat layers other than the hard-coat layer of this invention etc. are mentioned, for example. In addition, as a material which comprises said other layer, the above-mentioned plastic material etc. are mentioned, for example.

  Roughening treatment, adhesion facilitation treatment, antistatic treatment, sand blasting treatment (sand mat treatment), corona discharge treatment, plasma treatment, chemical etching treatment, water mat treatment, flame on a part or all of the surface of the plastic substrate Well-known or usual surface treatments, such as treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, silane coupling agent treatment, may be applied. In addition, an unstretched film may be sufficient as the said plastic base material, and a stretched film (a uniaxial stretched film, a biaxial stretched film, etc.) may be sufficient as it.

  The above-mentioned plastic substrate is, for example, a method of forming the above-mentioned plastic material into a film to form a plastic substrate (plastic film), and, if necessary, a layer suitable for the above-mentioned plastic film It can manufacture by the well-known thru | or conventional method, such as the method of forming a layer etc., or giving an appropriate surface treatment. In addition, a commercial item can also be used as said plastic base material.

  Although the thickness of the said base material is not specifically limited, For example, it can select suitably from the range of 0.01-10000 micrometers.

  The hard coat layer of the present invention in the hard coat film of the present invention is a layer constituting at least one surface layer in the hard coat film of the present invention, and the curable composition of the present invention (curable composition for forming hard coat layer) (The cured product layer) formed of the cured product (the cured resin product) obtained by curing the product.

  The thickness of the hard coat layer of the present invention (when the hard coat layer of the present invention is provided on both sides of the substrate, the thickness of each hard coat layer) is not particularly limited, but preferably 1 to 200 μm, more preferably 3 It is ̃150 μm. In particular, the hard coat layer of the present invention is capable of maintaining high surface hardness (e.g., setting the pencil hardness to H or more) even when thin (e.g., when the thickness is 5 [mu] m or less). . In addition, even when it is thick (for example, when the thickness is 50 μm or more), it is difficult to cause a defect such as a crack due to curing shrinkage etc., therefore, pencil hardness is significantly increased by thickening (for example, pencil hardness 9H or more) is possible.

  The haze of the hard coat layer of the present invention is not particularly limited, but in the case of a thickness of 50 μm, 1.5% or less is preferable, and 1.0% or less is more preferable. The lower limit of the haze is not particularly limited, and is, for example, 0.1%. By setting the haze to 1.0% or less in particular, for example, there is a tendency to be suitable for use in applications where very high transparency is required (for example, a surface protective sheet of a display such as a touch panel). The haze of the hard coat layer of the present invention can be measured in accordance with JIS K7136.

  The total light transmittance of the hard coat layer of the present invention is not particularly limited, but in the case of a thickness of 50 μm, 85% or more is preferable, and 90% or more is more preferable. The upper limit of the total light transmittance is not particularly limited, and is, for example, 99%. By making the total light transmittance 85% or more, for example, there is a tendency to be suitable for use in applications where very high transparency is required (for example, a surface protective sheet of a display such as a touch panel). The total light transmittance of the hard coat layer of the present invention can be measured in accordance with JIS K7361-1.

  The hard coat film of the present invention may further have a surface protective film on the surface of the hard coat layer of the present invention. The hard coat film of the present invention having a surface protective film tends to further improve the punching processability of the hard coat film. When the surface protective film is provided as described above, for example, such a problem occurs even if the hardness of the hard coat layer is very high and peeling or cracking from the base material is likely to occur during punching. It is possible to carry out punching using a Thomson blade without causing it.

  As the surface protective film, known or conventional surface protective films can be used, and although not particularly limited, for example, those having a pressure-sensitive adhesive layer on the surface of a plastic film can be used. Examples of the plastic film include polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyolefin (polyethylene, polypropylene, cyclic polyolefin, etc.), polystyrene, acrylic resin, polycarbonate, epoxy resin, fluorine resin, silicone resin, diacetate resin, Examples thereof include plastic films formed from plastic materials such as triacetate resin, polyarylate, polyvinyl chloride, polysulfone, polyether sulfone, polyether ether imide, polyimide, and polyamide. Examples of the pressure-sensitive adhesive layer include acrylic pressure-sensitive adhesives, natural rubber-based pressure-sensitive adhesives, synthetic rubber-based pressure-sensitive adhesives, ethylene-vinyl acetate copolymer-based pressure-sensitive adhesives, ethylene- (meth) acrylate copolymer-based pressure-sensitive adhesives Examples thereof include pressure-sensitive adhesive layers formed of one or more of known or commonly used pressure-sensitive adhesives such as styrene-isoprene block copolymer-based pressure-sensitive adhesives and styrene-butadiene block copolymer-based pressure-sensitive adhesives. The pressure-sensitive adhesive layer may contain various additives (for example, an antistatic agent, a slip agent, and the like). Each of the plastic film and the pressure-sensitive adhesive layer may have a single-layer structure, or may have a multilayer (multi-layer) structure. Moreover, the thickness of a surface protection film is not specifically limited, It can select suitably.

  As the surface protective film, for example, trade name "Sanitekto" series (manufactured by San Akaken Co., Ltd.), trade name "E-MASK" series (manufactured by Nitto Denko Corp.), trade name "Mastax" series (Fujimori Kogyo Co., Ltd. Commercial products such as those manufactured by Co., Ltd., trade name "Hitarex" series (made by Hitachi Chemical Co., Ltd.), trade name "Alfan" series (made by Oji F-Tex Co., Ltd.) are available from the market.

  The hard coat film of the present invention can be produced according to a known or commonly used method for producing a hard coat film, and the production method is not particularly limited. For example, the present invention The composition can be produced by applying a curable composition (hardenable composition for forming a hard coat layer) and optionally removing the solvent by drying and then curing the curable composition (curable composition layer) . The conditions for curing the curable composition are not particularly limited, and can be appropriately selected from the conditions for forming the above-mentioned cured product, for example.

  In particular, the hard coat layer of the present invention in the hard coat film of the present invention can be formed from the curable composition of the present invention (curable composition for forming a hard coat layer) capable of forming a cured product excellent in flexibility and processability. Because of the hard coat layer formed, the hard coat film of the present invention can be manufactured by a roll-to-roll method. By producing the hard coat film of the present invention by a roll-to-roll method, it is possible to remarkably improve the productivity. As a method for producing the hard coat film of the present invention by a roll-to-roll method, any known or commonly used roll-to-roll method can be adopted, and it is not particularly limited. Applying the curable composition (curable composition for forming a hard coat layer) of the present invention on at least one surface of the drawn-out substrate (step A) and the drawn-out substrate, and then, if necessary, drying the solvent The step of forming the hard coat layer of the present invention by curing the curable composition (curable composition layer) after removing by the step (step B), and thereafter, the obtained hard coat film is rolled again The method etc. which include the process (step C) of winding up as an essential process, and implement these processes (process AC) continuously are mentioned. In addition, the said method may include processes other than process AC.

  The thickness of the hard coat film of the present invention is not particularly limited, and can be appropriately selected from the range of 1 to 10000 μm.

  The pencil hardness of the hard coat layer surface of the hard coat film of the present invention is not particularly limited, but is preferably H or more, more preferably 2 H or more, and still more preferably 6 H or more. In addition, pencil hardness can be evaluated according to the method of JISK5600-5-4.

  The haze of the hard coat film of the present invention is not particularly limited, but is preferably 1.5% or less, more preferably 1.0% or less. The lower limit of the haze is not particularly limited, and is, for example, 0.1%. By setting the haze to 1.0% or less in particular, for example, there is a tendency to be suitable for use in applications where very high transparency is required (for example, a surface protective sheet of a display such as a touch panel). The haze of the hard coat film of the present invention can be easily controlled within the above range, for example, by using the above-mentioned transparent substrate as a substrate. The haze can be measured in accordance with JIS K7136.

  The total light transmittance of the hard coat film of the present invention is not particularly limited, but is preferably 85% or more, more preferably 90% or more. The upper limit of the total light transmittance is not particularly limited, and is, for example, 99%. By making the total light transmittance particularly 90% or more, for example, there is a tendency to be suitable for use in applications where very high transparency is required (for example, a surface protective sheet of a display such as a touch panel). The total light transmittance of the hard coat film of the present invention can be easily controlled within the above range, for example, by using the above-mentioned transparent substrate as a substrate. The total light transmittance can be measured in accordance with JIS K7361-1.

  The hard coat film of the present invention has flexibility and can be manufactured and processed by a roll-to-roll method while maintaining high hardness and high heat resistance, and thus has high quality and productivity. Also excellent. In particular, when the surface protective film is provided on the surface of the hard coat layer of the present invention, the punching processability is also excellent. For this reason, it can be preferably used for all the applications where such a characteristic is required. The hard coat film of the present invention can be used, for example, as a surface protection film in various products, a surface protection film in members or parts of various products, etc., and also used as a component of various products or their members or parts You can also Examples of the product include: display devices such as liquid crystal displays and organic EL displays; input devices such as touch panels: solar cells; various home appliances; various electric and electronic products; portable electronic terminals (for example, game machines, personal computers, tablets, Examples include various electric and electronic products such as smartphones and mobile phones, and various optical devices. Further, as an embodiment in which the hard coat film of the present invention is used as a component of various products and their members or parts, for example, a mode in which a hard coat film and a transparent conductive film in a touch panel are used. Be

  The cured product obtained by curing the curable composition of the present invention is excellent not only in the above-mentioned surface hardness, heat resistance, flexibility and processability but also excellent adhesion to an adherend. Exerts a sense of Therefore, the curable composition of the present invention can also be preferably used as an adhesive (sometimes referred to as "adhesive composition"). The adhesive obtained as the adhesive composition for the curable composition of the present invention is cured to an adhesive excellent in surface hardness, heat resistance, flexibility, processability, adhesiveness, and adhesiveness. Can be converted to The above-mentioned adhesive is, for example, a thermosetting adhesive when the curable composition of the present invention contains a photocationic polymerization initiator as a curing catalyst, and a thermosetting cationic polymerization initiator as a photocurable adhesive. It can be used as

  An adhesive sheet comprising at least a substrate and an adhesive layer on the substrate by using the curable composition (adhesive composition) of the present invention, wherein the adhesive layer is a cured product of the present invention An adhesive sheet (sometimes referred to as "the adhesive sheet of the present invention") that is a layer of the sex composition (sometimes referred to as the "adhesive layer of the present invention") can be obtained. The adhesive sheet of the present invention includes not only sheet-like but also sheet-like forms such as film-like, tape-like and plate-like. Although the adhesive sheet of the present invention is not particularly limited, it can be obtained, for example, by applying the curable composition of the present invention to a substrate and further, if necessary, drying. 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 adhesive sheet of the present invention may be a single-sided adhesive sheet having an adhesive layer only on one side of the substrate, or may be a double-sided adhesive sheet having an adhesive layer on both sides of the substrate. When the adhesive sheet of the present invention is a double-sided adhesive sheet, at least one adhesive layer may be the adhesive layer of the present invention, and the other may be the adhesive layer of the present invention, or other adhesive It may be an agent layer.

  As a substrate in the adhesive sheet of the present invention, a well-known and commonly used substrate (a substrate used in an adhesive sheet) can be used, and it is not particularly limited, but for example, plastic substrates, metal substrates, ceramic groups Materials, semiconductor substrates, glass substrates, paper substrates, wood substrates, substrates whose surfaces are coated surfaces, etc. Specifically, those similar to the substrate in the hard coat film of the present invention It is illustrated. Moreover, the base material in the adhesive sheet of this invention may be what is called a release liner, for example, the thing similar to the surface protection film in the hard coat film of this invention can also be used. The adhesive sheet of the present invention may have only one layer of the base material, or may have two or more layers. Moreover, the thickness of the said base material is not specifically limited, For example, it can select suitably in the range of 1-10000 micrometers.

  The adhesive sheet of the present invention may have only one layer of the adhesive layer of the present invention, or may have two or more types. Moreover, the thickness of the adhesive bond layer of this invention is not specifically limited, For example, it can select suitably in 0.1-10,000 micrometers. The same applies to the other adhesive layers (adhesive layers other than the adhesive layer of the present invention).

  The adhesive sheet of the present invention may have other layers (for example, an intermediate layer, an undercoat layer, etc.) in addition to the substrate and the adhesive layer.

  It is a laminate (laminate) constituted by three or more layers (at least three layers) by using the curable composition (composition for adhesives) of the present invention, which comprises two adherent layers, And at least an adhesive layer located between the adhesive layers (a layer for adhering the above-mentioned adhesive layers), the adhesive layer being a layer of a cured product of the curable composition of the present invention ("the adhesive of the present invention A laminate (sometimes referred to as a “layer of the present invention”) that is sometimes referred to as a layer can be obtained. The laminate of the present invention is not particularly limited, but, for example, the adhesive layer of the present invention is formed on one adhesive layer (for example, it can be formed similarly to the adhesive layer in the adhesive sheet of the present invention) It can obtain by bonding the other adhesion layer to the said adhesive bond layer, and hardening the adhesive bond layer of this invention by light irradiation, heating, etc. after that. In the laminate of the present invention, for example, when the adhesive sheet of the present invention is a single-sided adhesive sheet, the adhesive sheet of the present invention is bonded to an adherend layer and then the above adhesive sheet is irradiated with light or the like. It can be obtained by curing the adhesive layer of the present invention. In this case, a laminate is obtained in which the substrate in the adhesive sheet of the present invention is the adhesive layer. Furthermore, in the laminate of the present invention, for example, when the adhesive sheet of the present invention is a double-sided adhesive sheet and the substrate is a release liner, the adhesive sheet of the present invention is laminated to one adherend layer and peeled off. It can be obtained by peeling the liner, then bonding the other adhesive layer to the exposed adhesive layer, and then curing the adhesive layer of the present invention by light irradiation, heating or the like. However, the method for producing the laminate of the present invention is not limited to these methods.

  The adherend in the laminate of the present invention is not particularly limited, and examples thereof include the same as the substrate in the hard coat film of the present invention. The laminate of the present invention may have only two adherends, or may have three or more adherends. Moreover, the thickness of a to-be-adhered body is not specifically limited, For example, it can select suitably in the range of 1-100000 micrometers. The adherend may not have a strictly layered form.

  The laminate of the present invention may have only one layer of the adhesive layer of the present invention, or may have two or more. Moreover, the thickness of the adhesive layer of this invention is not specifically limited, For example, it can select suitably in the range of 0.1-10000 micrometers.

  The laminate of the present invention may have other layers (for example, an intermediate layer, an undercoat layer, other adhesive layers, etc.) in addition to the adherend and the adhesive layer of the present invention.

  The curable composition (composition for adhesives) of the present invention is not limited to the use for obtaining the adhesive sheet of the present invention described above or the laminate of the present invention, and bonds desired articles (parts etc.) It can be used for various applications.

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 H _HR L (manufactured by Tosoh Corporation), column oven: cOLUMN HEATER U-620 (manufactured by Sugai), the solvent was performed by 40 ° C.: THF, measuring conditions. Moreover, the measurement of the 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). The T _d5 (5% weight loss temperature) of the product was measured by TGA (thermogravimetric analysis) under an air atmosphere at a temperature elevation rate of 5 ° C./min.

  In addition, the compounding quantity of brand name "HS-1PC", "CPI-101A", "UV9380C", "HS-1A", and "SI-100L" was shown by the quantity of solid content conversion below.

Example 1
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter referred to as “EMS”) in a nitrogen stream to a 300 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube. ), 9 mmol (1.69 g) of phenyltrimethoxysilane (hereinafter referred to as “PMS”), and 165.9 g of acetone were charged, and the temperature was raised to 50 ° C. After adding 4.70 g of a 5% aqueous solution of potassium carbonate (1.7 mmol as potassium carbonate) dropwise over 5 minutes to the mixture thus obtained, 1700 mmol (30.60 g) of water was dropped over 20 minutes. . 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.
Analysis of the product in the reaction solution after the polycondensation reaction showed that 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 The product (epoxy group-containing polyorganosilsesquioxane) was obtained. The T _d5 of the above product was 370 ° C.

Examples 2 to 6, Comparative Examples 1 and 2 (Examples 4 and 5 are reference examples)
The amount of the raw materials (EMS and PMS) used, the type and amount of the solvent, the reaction temperature, the amount of the 5% aqueous solution of potassium carbonate, the amount of water used, and the reaction time as shown in Table 1 In the same manner as in 1, an epoxy group-containing polyorganosilsesquioxane was produced. Number average molecular weight (Mn), molecular weight dispersion degree, ratio of T3 body to T2 body [T3 body / T2 body], and T _d5 of epoxy group-containing polyorganosilsesquioxane obtained in each example are shown in Table 1 Indicated. The unit of T _{d5 in} Table 1 is “° C.”.

In addition, when the FT-IR spectrum of the polyorganosilsesquioxane obtained in Examples 1 to 6 was measured by the above-mentioned method, it was confirmed that each had one inherent absorption peak in the vicinity of 1100 cm ^-1 . .

Example 7
100 parts by weight of the epoxy group-containing polyorganosilsesquioxane (S-1) obtained in Example 1, 20 parts by weight of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.), and curing catalyst 1 ([diphenyl [4- A mixed solution of 1 part by weight of (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate] was prepared and used as a hard coat solution (curable composition).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 5 μm. The mixture was cast and cast, then allowed to stand (prebaked) in an oven at 70 ° C. for 10 minutes, and then irradiated with ultraviolet light (irradiation conditions (irradiation amount: 312 mJ / cm ² , irradiation intensity: 80 W / cm ² )). Finally, the coated film of the hard coat solution was cured by heat treatment (aging) at 80 ° C. for 2 hours to prepare a hard coat film having a hard coat layer.

Examples 8 to 17 and 19 and Comparative Examples 3 and 4 (Example 13 is a reference example)
A hard coat solution was produced in the same manner as in Example 7 except that the composition of the hard coat solution (curable composition) and the thickness of the hard coat layer were changed as shown in Table 2. A hard coat film was produced in the same manner as in Example 7 except that the hard coat solution was used and the thickness of the hard coat layer was changed as shown in Table 2. In addition, the unit of the compounding quantity of the raw material of the curable composition of Table 2 is a weight part.

Example 18
100 parts by weight of the epoxy group-containing polyorganosilsesquioxane (S-1) obtained in Example 1, 20 parts by weight of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.), and trade name "SI-100L" (thermal A mixed solution of 1 part by weight of an acid generator, manufactured by Sanshin Chemical Industry Co., Ltd., was prepared and used as a hard coat liquid (curable composition).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 25 μm. And cast, and then allowed to stand in an oven at 70 ° C. for 10 minutes, and then heat treated at 150 ° C. for 1 hour to thermally cure the coating film of the above-mentioned hard coating solution, thereby providing a hard coating having a hard coating layer A film was made.

  The hard coat film obtained above was subjected to various evaluations by the following method. The results are shown in Table 2.

(1) Haze and total light transmittance The haze and total light transmittance of the hard coat film obtained above were measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., NDH-300A).

(2) Surface hardness (pencil hardness)
The pencil hardness of the hard coat layer surface in the hard coat film obtained above was evaluated according to JIS K5600-5-4.

(3) Heat resistance (5% weight loss temperature (T _d5 ))
Using a cutter, the hard coat layer in the hard coat film obtained by the same method as described above except that a glass plate was used instead of the PET film, was used as a sample as a sample. The 5% weight loss temperature of the above sample was measured under the following conditions using a differential thermal gravimetric analyzer (manufactured by Seiko Instruments Inc., TG / DTA 6300).
Measurement temperature range: 25-550 ° C
Heating rate: 10 ° C / min Gas atmosphere: nitrogen

(4) Scratch resistance With respect to the hard coat layer surface in the hard coat film obtained above, # 0000 steel wool is reciprocated 100 times with a load of 1000 g / cm ² and the presence or absence of scratches attached to the hard coat layer surface Were evaluated, and the scratch resistance was evaluated according to the following criteria.
((Very good scratch resistance): 0 number of scratches ○ (good scratch resistance): 1 to 10 scratches × (poor scratch resistance): more than 10 scratches

(5) Flexibility (cylindrical mandrel method); Flexural resistance of the hard coat film obtained above by a mandrel test was evaluated according to JIS K5600-5-1 using a cylindrical mandrel.

The abbreviations shown in Table 2 are as follows. The sample name of polyorganosilsesquioxane corresponds to the sample name shown in Table 1.
Curing catalyst 1: [diphenyl [4- (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate], photo acid generator HS-1PC: trade name “HS-1PC” (manufactured by San-Apro Co., Ltd.), light Acid generator CPI-101A: trade name "CPI-101A" (San-Apro Co., Ltd. product), photo-acid generator UV 9380C: trade name "UV 9380 C" (momentive performance materials Japan Co., Ltd. product), photo acid Generator HS-1A: trade name "HS-1A" (San-Apro Co., Ltd.), photo acid generator SI-100 L: trade name "San-Aid SI-100 L" (sanshin Chemical Industry Co., Ltd.), thermal acid Generator

Example 20
A surface protective film (Mustrax NBO-0424 manufactured by Fujimori Kogyo Co., Ltd.) was attached to the surface of the hard coat layer of the hard coat film obtained in Example 14 to prepare a hard coat film having a surface protective film. About this hard coat film, punching was performed using a dumbbell sample cutter equipped with a super dumbbell cutter (type: SDK-500-D, in accordance with JIS K-7133-2 standard). As a result, it was confirmed that the hard coat film can be punched without peeling of the hard coat layer from the substrate and cracking of the hard coat layer.
FIG. 1 shows a photomicrograph (magnification: 100 times) of the end of the hard coat film after punching obtained as described above, which was taken with a digital microscope. As shown in FIG. 1, peeling of the hard coat layer from the substrate and cracking in the hard coat layer have not occurred.

Example 21
100 parts by weight of the epoxy group-containing polyorganosilsesquioxane (S-1) obtained in Example 1, 20 parts by weight of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.), and a trade name "HS-1 PC" A mixed solution of 1 part by weight of an acid generator and San-Apro Co., Ltd. was prepared and used as a hard coat liquid (curable composition).
Using the hard coat solution obtained above on a 78 μm thick TAC film (# 80, manufactured by Daicel Co., Ltd.), use a wire bar so that the thickness of the hard coat layer after curing is 50 μm. After cast coating, it was allowed to stand (prebaked) in an oven at 70 ° C. for 10 minutes and then irradiated with ultraviolet light (irradiation conditions (irradiation amount): 312 mJ / cm ² , irradiation intensity: 80 W / cm ² ). Finally, the coated film of the hard coat solution was cured by heat treatment (aging) at 80 ° C. for 2 hours to prepare a hard coat film having a hard coat layer.

Example 22
100 parts by weight of the epoxy group-containing polyorganosilsesquioxane (S-1) obtained in Example 1, 20 parts by weight of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.), and a trade name "HS-1 PC" A mixed solution of 1 part by weight of an acid generator and San-Apro Co., Ltd. was prepared and used as a hard coat liquid (curable composition).
The hard coat solution obtained above is applied to a 300 μm thick cycloolefin copolymer film (trade name “TOPAS 6013”, manufactured by Polyplastics Co., Ltd.), and the thickness of the hard coat layer after curing is 45 μm. After cast-coating using a wire bar, it was allowed to stand (prebaked) in an oven at 70 ° C. for 10 minutes and then irradiated with ultraviolet light (irradiation conditions (irradiation amount): 312 mJ / cm ² , irradiation intensity: 80 W / Cm ² ). Finally, the coated film of the hard coat solution was cured by heat treatment (aging) at 80 ° C. for 2 hours to prepare a hard coat film having a hard coat layer.

Example 23
100 parts by weight of the epoxy group-containing polyorganosilsesquioxane (S-1) obtained in Example 1, 20 parts by weight of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.), and a trade name "HS-1 PC" A mixed solution of 1 part by weight of an acid generator and San-Apro Co., Ltd. was prepared and used as a hard coat liquid (curable composition).
The hard coat solution obtained above was applied to a 2024 μm thick acrylic polymer film (trade name “Sumipex X, manufactured by Sumitomo Chemical Co., Ltd.) so that the thickness of the hard coat layer after curing was 32 μm. After cast coating using a wire bar, it was allowed to stand (prebaked) in an oven at 70 ° C. for 10 minutes and then irradiated with ultraviolet light (irradiation conditions (irradiation amount): 312 mJ / cm ² , irradiation intensity: 80 W / cm ² ). Finally, the coated film of the hard coat solution was cured by heat treatment (aging) at 80 ° C. for 2 hours to prepare a hard coat film having a hard coat layer.

Example 24
100 parts by weight of the epoxy group-containing polyorganosilsesquioxane (S-1) obtained in Example 1, 20 parts by weight of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.), and a trade name "HS-1 PC" A mixed solution of 1 part by weight of an acid generator and San-Apro Co., Ltd. was prepared and used as a hard coat liquid (curable composition).
The hard coat solution obtained above is formed on a 129 μm thick PEN film (trade name “Teonex # 125”, manufactured by Teijin DuPont Films Ltd.) so that the thickness of the hard coat layer after curing is 34 μm. The solution was cast coated using a wire bar, allowed to stand (prebaked) in an oven at 70 ° C. for 10 minutes, and then irradiated with ultraviolet light (irradiation conditions (irradiation amount): 312 mJ / cm ² , irradiation intensity: 80 W / cm ² ). Finally, the coated film of the hard coat solution was cured by heat treatment (aging) at 80 ° C. for 2 hours to prepare a hard coat film having a hard coat layer.

Example 25
100 parts by weight of the epoxy group-containing polyorganosilsesquioxane (S-1) obtained in Example 1, 20 parts by weight of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.), and a trade name "HS-1 PC" A mixed solution of 1 part by weight of an acid generator and San-Apro Co., Ltd. was prepared and used as a hard coat liquid (curable composition).
Using the hard coat solution obtained above on a 100 μm thick polycarbonate film (trade name “POLYCAACE”, manufactured by Sumitomo Bakelite Co., Ltd.), wire bar so that the thickness of the hard coat layer after curing becomes 45 μm The solution was cast and applied, and then allowed to stand (prebaked) in an oven at 70 ° C. for 10 minutes, and then irradiated with ultraviolet light (irradiation conditions (irradiation amount: 312 mJ / cm ² , irradiation intensity: 80 W / cm ² )) . Finally, the coated film of the hard coat solution was cured by heat treatment (aging) at 80 ° C. for 2 hours to prepare a hard coat film having a hard coat layer.

The haze, the total light transmittance, and the pencil hardness of the hard coat layer surface of the hard coat films obtained in Examples 21 to 25 were measured and evaluated. In addition, the haze, the total light transmittance, and the pencil hardness were measured and evaluated by the above-mentioned method.
In Table 3, the measurement and evaluation of the haze (for only the substrate), the total light transmittance, and the pencil hardness (surface of the substrate) of the substrate in the hard coat film obtained in Examples 21 to 25 The results are also shown.

  As shown in Tables 2 and 3, the hard coat film of the present invention has an extremely high surface hardness as compared to the substrate without the hard coat layer of the present invention, and is equivalent to the substrate The optical properties (transparency) were maintained. Furthermore, it was confirmed that various substrates can be applied as a substrate in the hard coat film of the present invention.

Example 26
2- (3,4-epoxy) cyclohexylethyltrimethoxysilane (EMS) in a nitrogen stream to a 5-liter separable flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube 1757.5 mmol (433.0 g), 93 mmol (18.34 g) of phenyltrimethoxysilane (PMS), and 1805.4 g of acetone were charged, and the temperature was raised to 50 ° C. After adding 51.14 g of a 5% aqueous solution of potassium carbonate (18.5 mmol as potassium carbonate) dropwise over 5 minutes to the mixture thus obtained, 18.5 moles (333.0 g) of water is added over 20 minutes. It dripped. Note that no significant temperature rise occurred during the dropping. Thereafter, the polycondensation reaction was performed for 5 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
The product in the reaction solution after the polycondensation reaction was analyzed to find that the number average molecular weight was 1800 and the molecular weight dispersion degree was 1.55. 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, while cooling the reaction solution, 902.7 g of methyl isobutyl ketone and 660 g of 5% saline solution were added and water washing was performed. After separation, the aqueous layer is removed, 902.7 g of methyl isobutyl ketone is again added, and the lower layer solution is washed with water until neutral, and the upper layer solution is separated, and the solvent is extracted from the upper layer solution under the conditions of 1 mmHg and 50 ° C. Is removed by distillation, and a colorless, transparent, liquid product containing 27.23% by weight of methyl isobutyl ketone (epoxy group-containing polyorganosilsesquioxane; polyorganosilsesquioxane containing 95 mol% of epoxy group and 5 mol% of phenyl group) ) Was obtained.

Example 27
2- (3,4-epoxy) cyclohexylethyltrimethoxysilane (EMS) in a nitrogen stream to a 5-liter separable flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube 200.0 mmol (49.29 g) and 197.1 g of acetone were charged, and the temperature was raised to 50.degree. To the mixture thus obtained, 5.53 g of a 5% aqueous solution of potassium carbonate (2.0 mmol as potassium carbonate) was added dropwise over 5 minutes, and then 2.0 moles (36.0 g) of water was added over 20 minutes. It dripped. Note that no significant temperature rise occurred during the dropping. Thereafter, the polycondensation reaction was performed for 5 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
Analysis of the product in the reaction solution after the polycondensation reaction revealed that the number average molecular weight was 1720 and the molecular weight dispersion degree was 1.55. The ratio of T2 body to T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the above product was 11.0.
Thereafter, while cooling the reaction solution, 98.4 g of methyl isobutyl ketone and 68.2 g of 5% saline were added and washed with water. After separation, the aqueous layer is removed, 98.4 g of methyl isobutyl ketone is again added, and the lower layer solution is washed with water until neutral, and the upper layer solution is separated, and the solvent is extracted from the upper layer solution under the conditions of 1 mmHg and 50 ° C. To give about 53 g of a colorless, transparent, liquid product (epoxy group-containing polyorganosilsesquioxane; 100 mol% of epoxy group polyorganosilsesquioxane) containing 33.78% by weight of methyl isobutyl ketone The

  [T3 body / T2 body] of silsesquioxane obtained in Example 26 is 10.3, and [T3 body / T2 body] of silsesquioxane obtained in Example 27 is 11.3. It was 0, and it was confirmed that T2 body existed in part in all.

Example 28
2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane (EMS) 237. under a stream of nitrogen into a 500 ml flask (reaction vessel) fitted with a thermometer, stirrer, reflux condenser, and nitrogen inlet tube. 5 mmol (58.52 g), 13 mmol (2.95 g) of 3-glycidyloxypropyltrimethoxysilane (hereinafter referred to as "GMS"), and 245.9 g of acetone were charged, and the temperature was raised to 50 ° C. After adding 6.91 g of 5% aqueous potassium carbonate solution (2.5 mmol as potassium carbonate) dropwise over 5 minutes to the mixture thus obtained, 2500 mmol (45.00 g) of water was dropped over 20 minutes. . Note that no significant temperature rise occurred during the dropping. Thereafter, the polycondensation reaction was performed for 5 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
Analysis of the product in the reaction solution after the polycondensation reaction revealed that the number average molecular weight was 1782, and the molecular weight dispersion degree was 1.52. The ratio of T2 form to T3 form [T3 form / T2 form] calculated from the ²⁹ Si-NMR spectrum of the above product was 9.5 / 1.
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 50 ° C. 60 g of a colorless and transparent liquid product (epoxy group-containing polyorganosilsesquioxane) was obtained.

Example 29
In a 500 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (EMS) 200. 0 mmol (49.28 g), 50 mmol (11.82 g) of 3-glycidyloxypropyltrimethoxysilane (GMS), and 244.4 g of acetone were charged, and the temperature was raised to 50 ° C. After adding 6.91 g of 5% aqueous potassium carbonate solution (2.5 mmol as potassium carbonate) dropwise over 5 minutes to the mixture thus obtained, 2500 mmol (45.00 g) of water was dropped over 20 minutes. . Note that no significant temperature rise occurred during the dropping. Thereafter, the polycondensation reaction was performed for 5 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
The product in the reaction solution after the polycondensation reaction was analyzed to find that the number average molecular weight was 1725 and the molecular weight dispersity 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 10.5 / 1.
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 50 ° C. 60 g of a colorless and transparent liquid product (epoxy group-containing polyorganosilsesquioxane) was obtained.

Example 30
In a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (EMS) 150 under a nitrogen stream. 0 mmol (36.96 g), 350 mmol (82.72 g) of 3-glycidyloxypropyltrimethoxysilane (GMS), and 478.7 g of acetone were charged, and the temperature was raised to 50 ° C. After 13.82 g of a 5% aqueous solution of potassium carbonate (5 mmol as potassium carbonate) was added dropwise over 5 minutes to the mixture thus obtained, 5000 mmol (90.00 g) of water was added dropwise over 20 minutes. Note that no significant temperature rise occurred during the dropping. Thereafter, the polycondensation reaction was performed for 5 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
Analysis of the product in the reaction solution after the polycondensation reaction revealed that the number average molecular weight was 1,500 and the molecular weight dispersity was 1.36. The ratio of T2 body to T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the above product was 8/1.
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 50 ° C. There were obtained 114 g of a colorless and transparent liquid product (epoxy group-containing polyorganosilsesquioxane).

Example 31
In a 6 cc brown-brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 27.23% by weight] obtained in Example 26; trade name “WPI-124” (Wako Pure Chemical Industries, Ltd. ), 50% solution of photo acid generator) 14.6 mg [14.6 mg as a 50% solution], trade name "BYK-307" (manufactured by Bick Chemie Co., Ltd., leveling agent) 1.5 mg, and methyl isobutyl ketone 0.253 g was added and stirred and mixed by a vibrator to prepare a curable composition (hard coating solution).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 30 μm. The mixture was cast and cast, then allowed to stand (prebaked) in an oven at 70 ° C. for 10 minutes, and then irradiated with ultraviolet light (irradiation conditions (irradiation amount): 430 mJ / cm ² , irradiation intensity: 160 W / cm ² ). Finally, the coated film of the hard coat solution was cured by heat treatment (aging) at 80 ° C. for 2 hours to prepare a hard coat film having a hard coat layer.

  In addition, the unit of the compounding quantity of the raw material of the curable composition of Table 4 and Table 5 is a weight part. In addition, “silsesquioxane obtained in Example 26”, “silsesquioxane obtained in Example 27”, “silsesquioxane obtained in Example 28” in Tables 4 and 5; The compounding amounts of “silsesquioxane obtained in Example 29” and “silsesquioxane obtained in Example 30” are shown as amounts excluding MIBK. Furthermore, the compounding quantity of "WPI-124" in Table 4 and Table 5 was shown as the quantity except the solvent. In Tables 4 and 5, the content of the solvent is omitted.

Example 32
The thickness of the hard coat layer after curing is 30 μm on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Film Co., Ltd.) and the curable composition (hard coat liquid) prepared in Example 31 After cast-coating using a wire bar, it was allowed to stand (prebaked) in an oven at 70 ° C. for 10 minutes, and then irradiated with ultraviolet rays (irradiation conditions (irradiation amount): 430 mJ / cm ² , irradiation intensity: 160 W / The coated film of the above hard coating solution was cured by conducting (cm ² ) (without subsequent heat treatment) to prepare a hard coated film having a hard coated layer.

Example 33
In a 6 cc brown-brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 27.23% by weight] obtained in Example 26; trade name “WPI-124” (Wako Pure Chemical Industries, Ltd. ), 50% solution of photo acid generator) 14.6 mg [14.6 mg as a 50% solution], trade name "BYK-307" (manufactured by Bick Chemie Co., Ltd., leveling agent) 1.5 mg, methyl isobutyl ketone 0 .253 g and 36.4 mg of ethylene glycol monovinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and mixed by stirring with a vibrator to prepare a curable composition (hard coat liquid).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 30 μm. after casting and coating and, allowed to stand for 10 minutes in an oven at 70 ° C. and (prebaked), followed by irradiation with ultraviolet rays (irradiation conditions (dose): 155mJ / cm ^2, irradiation intensity: 160 W / cm ²⁾ by The coated film of the hard coating solution was cured (without the subsequent heat treatment) to produce a hard coated film having a hard coating layer.

Example 34
In a 6 cc brown-brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 33.78% by weight] obtained in Example 27; trade name "WPI-124" (Wako Pure Chemical Industries, Ltd. Made in a 50% solution of a photoacid generator) 13.2 mg [13.2 mg as a 50% solution], trade name "BYK-307" (Bick Chemie Co., Ltd., leveling agent) 1, 3 mg, methyl isobutyl ketone 0 .104 g and 33.1 mg of ethylene glycol monovinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and mixed by stirring with a vibrator to prepare a curable composition (hard coat liquid).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 30 μm. after casting and coating and, allowed to stand for 10 minutes in an oven at 70 ° C. and (prebaked), followed by irradiation with ultraviolet rays (irradiation conditions (dose): 155mJ / cm ^2, irradiation intensity: 160 W / cm ²⁾ by The coated film of the hard coating solution was cured (without the subsequent heat treatment) to produce a hard coated film having a hard coating layer.

Example 35
In a 6 cc brown-brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 33.78% by weight] obtained in Example 27; trade name "WPI-124" (Wako Pure Chemical Industries, Ltd. Made in a 50% solution of a photoacid generator) 13.2 mg [13.2 mg as a 50% solution], trade name “BYK-307” (Bick Chemie Co., Ltd., leveling agent) 1.3 mg, methyl isobutyl ketone 0 After adding .104 g and 33.1 mg of cyclohexanedimethanol monovinyl ether, the mixture was stirred and mixed by a vibrator to prepare a curable composition (hard coat liquid).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 30 μm. after casting and coating and, allowed to stand for 10 minutes in an oven at 70 ° C. and (prebaked), followed by irradiation with ultraviolet rays (irradiation conditions (dose): 155mJ / cm ^2, irradiation intensity: 160 W / cm ²⁾ by The coated film of the hard coating solution was cured (without the subsequent heat treatment) to produce a hard coated film having a hard coating layer.

Example 36
In a 6 cc brown-brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 33.78% by weight] obtained in Example 27; trade name "WPI-124" (Wako Pure Chemical Industries, Ltd. Made in a 50% solution of a photoacid generator) 13.2 mg [13.2 mg as a 50% solution], trade name “BYK-307” (Bick Chemie Co., Ltd., leveling agent) 1.3 mg, methyl isobutyl ketone 0 After adding .104 g and 33.1 mg of triethylene glycol monovinyl ether, the mixture was stirred and mixed by a vibrator to prepare a curable composition (hard coating solution).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 30 μm. after casting and coating and, allowed to stand for 10 minutes in an oven at 70 ° C. and (prebaked), followed by irradiation with ultraviolet rays (irradiation conditions (dose): 155mJ / cm ^2, irradiation intensity: 160 W / cm ²⁾ by The coated film of the hard coating solution was cured (without the subsequent heat treatment) to produce a hard coated film having a hard coating layer.

Example 37
In a 6 cc brown-brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 33.78% by weight] obtained in Example 27; trade name "WPI-124" (Wako Pure Chemical Industries, Ltd. Made in a 50% solution of a photoacid generator) 13.2 mg [13.2 mg as a 50% solution], trade name “BYK-307” (Bick Chemie Co., Ltd., leveling agent) 1.3 mg, methyl isobutyl ketone 0 After adding .104 g and 33.1 mg of diethylene glycol monovinyl ether, the mixture was stirred and mixed by a vibrator to prepare a curable composition (hard coat liquid).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 30 μm. after casting and coating and, allowed to stand for 10 minutes in an oven at 70 ° C. and (prebaked), followed by irradiation with ultraviolet rays (irradiation conditions (dose): 155mJ / cm ^2, irradiation intensity: 160 W / cm ²⁾ by The coated film of the hard coating solution was cured (without the subsequent heat treatment) to produce a hard coated film having a hard coating layer.

Example 38
In a 6 cc brown-brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 33.78% by weight] obtained in Example 27; trade name "WPI-124" (Wako Pure Chemical Industries, Ltd. Made in a 50% solution of a photoacid generator) 13.2 mg [13.2 mg as a 50% solution], trade name “BYK-307” (Bick Chemie Co., Ltd., leveling agent) 1.3 mg, methyl isobutyl ketone 0 After adding .104 g and 33.1 mg of hydroxybutyl vinyl ether, the mixture was stirred and mixed with a vibrator to prepare a curable composition (hard coating solution).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 30 μm. after casting and coating and, allowed to stand for 10 minutes in an oven at 70 ° C. and (prebaked), followed by irradiation with ultraviolet rays (irradiation conditions (dose): 155mJ / cm ^2, irradiation intensity: 160 W / cm ²⁾ by The coated film of the hard coating solution was cured (without the subsequent heat treatment) to produce a hard coated film having a hard coating layer.

Example 39
In a 6 cc brown-brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 33.78% by weight] obtained in Example 27; trade name "WPI-124" (Wako Pure Chemical Industries, Ltd. Made in a 50% solution of a photoacid generator) 13.2 mg [13.2 mg as a 50% solution], trade name “BYK-307” (Bick Chemie Co., Ltd., leveling agent) 1.3 mg, methyl isobutyl ketone 0 After adding .104 g and 33.1 mg of isobutyl vinyl ether, the mixture was stirred and mixed by a vibrator to prepare a curable composition (hard coating solution).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 30 μm. after casting and coating and, allowed to stand for 10 minutes in an oven at 70 ° C. and (prebaked), followed by irradiation with ultraviolet rays (irradiation conditions (dose): 155mJ / cm ^2, irradiation intensity: 160 W / cm ²⁾ by The coated film of the hard coating solution was cured (without the subsequent heat treatment) to produce a hard coated film having a hard coating layer.

Example 40
In a 6 cc brown-brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 33.78% by weight] obtained in Example 27; trade name "WPI-124" (Wako Pure Chemical Industries, Ltd. Made in a 50% solution of a photoacid generator) 13.2 mg [13.2 mg as a 50% solution], trade name “BYK-307” (Bick Chemie Co., Ltd., leveling agent) 1.3 mg, methyl isobutyl ketone 0 After adding .104 g and 33.1 mg of cyclohexanedimethanol divinyl ether, the mixture was stirred and mixed by a vibrator to prepare a curable composition (hard coat liquid).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 30 μm. after casting and coating and, allowed to stand for 10 minutes in an oven at 70 ° C. and (prebaked), followed by irradiation with ultraviolet rays (irradiation conditions (dose): 155mJ / cm ^2, irradiation intensity: 160 W / cm ²⁾ by The coated film of the hard coating solution was cured (without the subsequent heat treatment) to produce a hard coated film having a hard coating layer.

Example 41
In a 6 cc brown-brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 33.78% by weight] obtained in Example 26; trade name "WPI-124" (Wako Pure Chemical Industries, Ltd. Made in a 50% solution of a photoacid generator) 13.2 mg [13.2 mg as a 50% solution], trade name “BYK-307” (Bick Chemie Co., Ltd., leveling agent) 1.3 mg, methyl isobutyl ketone 0 After adding .104 g and 33.1 mg of diethylene glycol divinyl ether, the mixture was stirred and mixed by a vibrator to prepare a curable composition (hard coat liquid).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 30 μm. after casting and coating and, allowed to stand for 10 minutes in an oven at 70 ° C. and (prebaked), followed by irradiation with ultraviolet rays (irradiation conditions (dose): 155mJ / cm ^2, irradiation intensity: 160 W / cm ²⁾ by The coated film of the hard coating solution was cured (without the subsequent heat treatment) to produce a hard coated film having a hard coating layer.

Example 42
A wire bar was prepared so that the hard coat layer obtained in Example 31 had a thickness of 30 μm after curing on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Films Ltd.). The solution is cast and applied, and then left (prebaked) in an oven at 70 ° C. for 10 minutes, and then irradiated with ultraviolet light (irradiation condition (irradiation amount): 155 mJ / cm ² , irradiation intensity: 160 W / cm ² ) Accordingly (without subsequent heat treatment), the coating film of the hard coating solution was cured to prepare a hard coating film having a hard coating layer.

Example 43
A hard coat film was produced under the same procedure and conditions as in Example 34 except that no vinyl ether compound was added as a constituent of the hard coat solution.

Example 44
In a 6 cc brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 17.81% by weight] obtained in Example 28; trade name "WPI-124" (Wako Pure Chemical Industries, Ltd. (A 50% solution of a photoacid generator) 16.4 mg [16.4 mg as a 50% solution], trade name "BYK-307" (manufactured by Bick Chem., Ltd., leveling agent), and methyl isobutyl ketone 0.2. 37 g was added and stirred and mixed by a vibrator to prepare a curable composition (hard coating solution).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Film Co., Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 40 μm. The mixture was cast and cast, then allowed to stand (prebaked) in an oven at 70 ° C. for 10 minutes, and then irradiated with ultraviolet light (irradiation conditions (irradiation amount): 430 mJ / cm ² , irradiation intensity: 160 W / cm ² ). Thereafter, the coated film of the above-mentioned hard coating solution was cured by being left (post-baked) in an oven at 80 ° C. for 2 hours to produce a hard coated film having a hard coating layer.

Example 45
In a 6 cc brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 25.84% by weight] obtained in Example 29; trade name "WPI-124" (Wako Pure Chemical Industries, Ltd. 14.8 mg [as a 50% solution, 14.8 mg], trade name “BYK-307” (manufactured by Bick Chem., Ltd., leveling agent), and methyl isobutyl ketone 0. The mixture was stirred with a vibrator and mixed to prepare a curable composition (hard coating solution).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Film Co., Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 40 μm. The mixture was cast and cast, then allowed to stand (prebaked) in an oven at 70 ° C. for 10 minutes, and then irradiated with ultraviolet light (irradiation conditions (irradiation amount): 430 mJ / cm ² , irradiation intensity: 160 W / cm ² ). Thereafter, the coated film of the above-mentioned hard coating solution was cured by being left (post-baked) in an oven at 80 ° C. for 2 hours to produce a hard coated film having a hard coating layer.

Example 46
In a 6 cc brown sample bottle, 1 g of epoxy group-containing polyorganosilsesquioxane [1 g as a content of MIBK 26.36% by weight] obtained in Example 30; trade name "WPI-124" (Wako Pure Chemical Industries, Ltd. A 50% solution of a photoacid generator) 14.7 mg [14.7 mg as a 50% solution], trade name "BYK-307" (manufactured by Bick Chem., Ltd., leveling agent), and methyl isobutyl ketone 0.2. After putting 23 g, the mixture was stirred and mixed by a vibrator to prepare a curable composition (hard coating solution).
The hard coat solution obtained above is used on a PET film (trade name “KEB03 W”, manufactured by Teijin DuPont Film Co., Ltd.) using a wire bar so that the thickness of the hard coat layer after curing is 40 μm. The mixture was cast and cast, then allowed to stand (prebaked) in an oven at 70 ° C. for 10 minutes, and then irradiated with ultraviolet light (irradiation conditions (irradiation amount): 430 mJ / cm ² , irradiation intensity: 160 W / cm ² ). Thereafter, the coated film of the above-mentioned hard coating solution was cured by being left (post-baked) in an oven at 80 ° C. for 2 hours to produce a hard coated film having a hard coating layer.

  About each hard coat film obtained in Examples 31-46, various evaluation was performed by the following methods. The results are shown in Tables 4 and 5.

(1) Haze and total light transmittance The haze and total light transmittance of the hard coat film were measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., NDH-300A).

(2) Yellowness b ^*
The yellowness b ^* of the hard coat film was measured using a color difference meter (NDH-300A, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

(3) Surface hardness (pencil hardness)
The pencil hardness of the surface of the hard coat layer in the hard coat film was evaluated according to JIS K5600-5-4.

(4) Heated yellowing after curing The hard coat films obtained in Examples 34 to 41 are subjected to heat treatment at the heating temperature and heating time described in the column "Heating yellowing after curing" in Table 4, The yellowness b ^* of the hard coat film after that was measured using a color difference meter (NDH-300A manufactured by Nippon Denshoku Kogyo Co., Ltd.). The results are shown in Table 4.

The abbreviations shown in Tables 4 and 5 are as follows.
EGVE: ethylene glycol monovinyl ether CHXDM-VE: cyclohexanedimethanol monovinyl ether TEG-VE: triethylene glycol monovinyl ether DEG-VE: diethylene glycol monovinyl ether HBVE: hydroxybutyl vinyl ether IBVE: isobutyl vinyl ether CHXDMDVE: cyclohexane dimethanol divinyl ether DEGDVE: diethylene glycol Divinyl ether WPI-124: trade name "WPI-124", manufactured by Wako Pure Chemical Industries, Ltd., 50% solution of photoacid generator

As shown in Tables 4 and 5, all of the hard coat films (Examples 31 to 46) of the present invention had high surface hardness and were also excellent in transparency.
In particular, when a vinyl ether compound is used in combination as a cationically curable compound (for example, Examples 33 to 41), ultraviolet irradiation is performed as compared with the case where a vinyl ether compound is not used in combination (for example, Examples 31, 32, 42, 43). Even at low amounts, hard coat films having very high surface hardness were obtained. Therefore, by using a vinyl ether compound in combination as a cationically curable compound, the line speed can be further increased in the production, and a hard coat film can be produced with very excellent productivity.
Furthermore, when a vinyl ether compound having a hydroxyl group is used in combination as a cationically curable compound (for example, Examples 34 to 38), a vinyl ether compound having no hydroxyl group is used in combination (for example, Example 39 to 41) It is possible to produce a hard coat film having higher surface hardness and further excellent in heat resistance yellowing.

Note that each of the hard coat film obtained in Example 31 to 46 was evaluated for heat resistance (T _d5) and flexibility in the manner described above, both T _d5 is excellent in heat resistance comprising at 380 ° C. or higher The results of the mandrel test were all 25 mm or less in diameter at a film thickness of 30 μm of the hard coat layer, and also excellent in flexibility and processability.

Example 47
(Preparation of adhesive composition)
100 parts by weight of the epoxy group-containing polyorganosilsesquioxane (S-1) (cationically polymerizable compound) obtained in Example 1, 50 parts by weight of propylene glycol monomethyl ether acetate, trade name "Sanaid SI-150L" 0.1 parts by weight of an antimonial sulfonium salt, manufactured by Shin Chemical Industry Co., Ltd., and a trade name “San-Aid SI aid” (manufactured by Sanshin Chemical Industries, Ltd., (4-hydroxyphenyl) dimethylsulfonium methyl sulfite) 3.) 0.005 parts by weight was mixed to obtain an adhesive composition (adhesive composition).

Example 48
(Preparation of adhesive layer)
A silane coupling agent (trade name "KBE 403", Shin-Etsu Chemical Co., Ltd.) is applied by spin coating on one side of a glass plate (4 inches, SCHOTT made by Japan Ltd.) and heated at 100 ° C for 15 minutes Further, the adhesive composition obtained in Example 47 is applied by spin coating, and then heated at 60 ° C. for 10 minutes to prepare an adhesive layer having a film thickness of 5 μm, and a glass plate with an adhesive layer (“ (Layer structure of glass plate / silane coupling agent layer / adhesive layer) was obtained.

(Preparation of Silane Coupling Agent Layer)
A silane coupling agent (trade name "KBE 403", Shin-Etsu Chemical Co., Ltd.) is spin coated on one side of a glass plate (4 inches, SCHOTT made by Japan Ltd.) and heated at 100 ° C for 15 minutes. A silane coupling agent layer was produced to obtain a glass plate with a silane coupling agent layer (having a layer configuration of "glass plate / silane coupling agent layer").

(Production of adhesive (laminated body))
The glass plate with an adhesive layer obtained above and the glass plate with a silane coupling agent layer obtained above are set to 60 ° C. so that the former adhesive layer and the latter silane coupling agent layer face each other. Adhesive body by applying a pressure of 200 g / cm ² while heating, heating at 150 ° C. for 30 minutes, and then heating at 170 ° C. for 30 minutes (laminate; “glass plate / silane coupling Agent layer / cured material layer of adhesive composition (adhesive layer) / silane coupling agent layer / glass plate) was obtained.

  The following evaluation was performed about the composition for adhesive agents and adhesive body (laminate) which were obtained above.

(Evaluation of adhesion)
The adhesion of the coating film (adhesive layer) obtained using the adhesive composition obtained in Example 47 was evaluated by the cross cut tape test according to JIS K5400-8.5. In addition, as a sample, what was obtained by heating the adhesive layer-coated glass plate prepared in Example 48 at 150 ° C. for 30 minutes and then heating at 170 ° C. for 30 minutes was used (that is, the coating film was Example 47, the cured product layer of the adhesive composition obtained in Example 47).
As a result of the cross-cut tape test, no peeling of the coating film from the glass plate (having a layer constitution of "glass plate / silane coupling agent layer") is observed, and the coating film has excellent adhesion. confirmed.

(Adhesive evaluation)
When a razor blade is inserted into the adhesive interface of the adhesive body (laminate) obtained in Example 48, no peeling on the adhesive surface occurs, and it is confirmed that the adhesive layer in the adhesive body has excellent adhesiveness. The

Claims (9)

Following formula (1)
[In Formula (1), R ¹ represents a group containing an epoxy group. ]
And a structural unit represented by the following formula (2)
[In Formula (2), R ² represents a substituted or unsubstituted aryl group. ]
And a structural unit represented by formula (I) below
[In Formula (I), R ^a represents a group containing an epoxy group, or a substituted or unsubstituted aryl group . ]
And a structural unit represented by the following formula (II)
[In Formula (II), R ^b represents a group containing an epoxy group, or a substituted or unsubstituted aryl group . R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The molar ratio of the structural unit represented by [structural unit represented by formula (I) / structural unit represented by formula (II)] is 5 or more and 11 or less, and the total amount (100 mol%) of the siloxane structural unit The structural unit represented by the above formula (1) for
[In Formula (4), R ¹ is the same as in Formula (1). R ^c is the same as in formula (II). ]
The proportion of the structural unit represented by is 95 mol% or more and less than 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion degree (weight average molecular weight / number average molecular weight) is 1.0 to 3.0. Polyorganosilsesquioxane characterized by
Here, the molar ratio [constituent unit represented by formula (I) / constituent unit represented by formula (II)] is the formula (I) in the ²⁹ Si-NMR spectrum of the polyorganosilsesquioxane. The integral value of the peak of the silicon atom in the constituent unit represented by () and the integral value of the peak of the silicon atom in the constituent unit represented by the above formula (II) are measured, and calculated according to the following formula.
Said R ¹ is a following formula (1a)
[In Formula (1a), R ^1a represents a linear or branched alkylene group. ]
A group represented by the following formula (1b)
[In Formula (1b), R ^1b represents a linear or branched alkylene group. ]
A group represented by the following formula (1c)
[In Formula (1c), R ^1c represents a linear or branched alkylene group. ]
Or a group represented by the following formula (1d)
[In Formula (1d), R ^1d represents a linear or branched alkylene group. ]
The polyorganosilsesquioxane according to claim 1, which is a group represented by A curable composition comprising the polyorganosilsesquioxane according to claim 1 or 2 . The curable composition according to claim 3 , further comprising a curing catalyst. The curable composition according to claim 4 , wherein the curing catalyst is a photocationic polymerization initiator. The curable composition according to claim 4 , wherein the curing catalyst is a thermal cationic polymerization initiator. The curable composition according to any one of claims 3 to 6 , further comprising a vinyl ether compound. The curable composition according to any one of claims 3 to 7 , further comprising a vinyl ether compound having a hydroxyl group in the molecule. A cured product of the curable composition according to any one of claims 3 to 8 .