阅读说明：本技术 树脂组合物、硬涂薄膜以及聚有机硅倍半氧烷 (Resin composition, hard coating film and polyorganosilsesquioxane ) 是由 永田裕三 芥川畅之 北村哲 田村显夫 于 2020-05-11 设计创作，主要内容包括：本发明提供树脂组合物、包含将上述树脂组合物固化而得到的硬涂层的硬涂薄膜以及聚有机硅倍半氧烷,该树脂组合物含有聚有机硅倍半氧烷,该聚有机硅倍半氧烷具有含有能够形成氢键的氢原子的基团,该树脂组合物中,上述聚有机硅倍半氧烷的氢键值为3.0以上,侧链长度为14×10～(-10)～19×10～(-10)m,以及上述聚有机硅倍半氧烷的氢键值为3.0以上,交联性基团值为4.5～6.0。(The invention provides a resin composition, a hard coating film comprising a hard coating layer obtained by curing the resin composition, and a polyorgano silsesquioxane, wherein the resin composition comprises a polyorgano silsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond, and the polyorgano silsesquioxaneThe silsesquioxane has hydrogen bond value of 3.0 or more and side chain length of 14 × 10 ‑10 ～19×10 ‑10 m, and the polyorganosilsesquioxane has a hydrogen bond value of 3.0 or more and a crosslinkable group value of 4.5 to 6.0.)

1. A resin composition comprising a polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond,

the polyorganosilsesquioxane has a hydrogen bond value of 3.0 or more and a side chain length of 14X 10^-10～19×10^-10m，

The hydrogen bond value is represented by the following formula (1), the side chain length represents a length from the Si atom to the end of the side chain,

hydrogen value ═ 1 number of hydrogen atoms capable of forming hydrogen bonds in the structural unit/1 molecular weight of the structural unit × 1000 (1).

2. A resin composition comprising a polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond,

the polyorganosilsesquioxane has a hydrogen bond value of 3.0 or more and a crosslinkable group value of 4.5 to 6.0,

the hydrogen bond value is represented by the following formula (1), the crosslinkable group value is represented by the following formula (5),

the number of hydrogen atoms capable of forming hydrogen bonds among 1 structural unit/molecular weight of 1 structural unit × 1000 (1),

the value of the crosslinkable group is 1 number of crosslinkable groups in the structural unit/molecular weight of 1 structural unit × 1000 (5).

3. The resin composition according to claim 1 or 2, wherein,

the polyorganosilsesquioxane has a hydrogen bond value of 3.0 or more and a side chain length of 14X 10^-10～19×10^-10m, a crosslinkable group value of 4.5 to 6.0.

4. The resin composition according to any one of claims 1 to 3, wherein,

the group containing a hydrogen atom capable of forming a hydrogen bond is at least one group selected from an amide group, a urethane group, a urea group and a hydroxyl group.

5. The resin composition according to any one of claims 1 to 4, wherein,

the polyorganosilsesquioxane contains: a structural unit having a group containing a hydrogen atom capable of forming a hydrogen bond (S1); and a structural unit (S2) having a crosslinkable group, which is different from the structural unit (S1).

6. The resin composition according to claim 5, wherein,

the group containing a hydrogen atom capable of forming a hydrogen bond in the structural unit (S1) is at least one group selected from an amide group, a urethane group and a urea group.

7. The resin composition according to claim 5 or 6, wherein,

the structural unit (S1) further has a crosslinkable group, which is a (meth) acryloyloxy group or a (meth) acrylamide group.

8. The resin composition according to any one of claims 5 to 7, wherein,

the crosslinkable group of the structural unit (S2) is a (meth) acrylamide group.

9. The resin composition according to any one of claims 1 to 8, wherein,

the weight average molecular weight of the polyorganosilsesquioxane is 10000-1000000.

10. A hardcoat film having: a substrate; and a hard coat layer comprising a cured product of the resin composition according to any one of claims 1 to 9.

11. The hardcoat film of claim 10 wherein,

the pencil hardness is 3H or more, and cracks are not generated when the 180 DEG bending test is repeatedly performed for 10 ten thousand times with the base material as the inner side and the curvature radius of 2 mm.

12. A polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond, wherein,

hydrogen number of 3.0 or more and side chain length of 14X 10^-10～19×10^-10m，

The hydrogen bond value is represented by the following formula (1), the side chain length represents a length from a Si atom to a side chain terminal,

hydrogen value ═ 1 number of hydrogen atoms capable of forming hydrogen bonds in the structural unit/1 molecular weight of the structural unit × 1000 (1).

13. A polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond, wherein,

a hydrogen bond value of 3.0 or more, a crosslinkable group value of 4.5 to 6.0,

the hydrogen bond value is represented by the following formula (1), the crosslinkable group value is represented by the following formula (5),

the number of hydrogen atoms capable of forming hydrogen bonds among 1 structural unit/molecular weight of 1 structural unit × 1000 (1),

the value of the crosslinkable group is 1 number of crosslinkable groups in the structural unit/molecular weight of 1 structural unit × 1000 (5).

14. The polyorganosilsesquioxane according to claim 12 or 13,

hydrogen number of 3.0 or more and side chain length of 14X 10^-10～19×10^-10m, a crosslinkable group value of 4.5 to 6.0.

Technical Field

The present invention relates to a resin composition, a hard coat film having a hard coat layer obtained by curing the resin composition, and a polyorganosilsesquioxane.

Background

In image display devices such as display devices using Cathode Ray Tubes (CRTs), Plasma Displays (PDPs), electroluminescence displays (ELDs), fluorescent displays (VFDs), Field Emission Displays (FEDs), and Liquid Crystal Displays (LCDs), it is preferable to provide a hard coating film having a hard coating layer on a substrate in order to prevent damage to the display surface.

As a resin composition for forming a hard coat layer, a resin composition containing a polyorganosilsesquioxane is known.

For example, patent document 1 describes an active energy ray-curable composition containing a silsesquioxane compound that is an organic group having at least one urea bond and 1 (meth) acryloyloxy group among organic groups directly bonded to silicon atoms. Patent document 2 describes a liquid coating agent mixture containing a compound obtained by hydrolyzing and condensing an organosilane having a UV-curable group, a thermosetting silyl group, and a crosslinking group having at least 2 carbon atoms bonding the UV-curable group and the thermosetting silyl group.

Prior art documents

Patent document

Patent document 1: international publication No. 2010/067685 specification

Patent document 2: japanese Kohyo publication 2011-518666

Disclosure of Invention

Technical problem to be solved by the invention

In recent years, for example, in smart phones and the like, demands for extremely thin flexible displays have been increasing, and accordingly, there is a strong demand for an optical film that can combine hardness and resistance to repeated bending (a property that cracks do not occur even when repeatedly bent).

As a result of studies, the inventors of the present invention have found that a hard coat film using the resin compositions described in patent documents 1 and 2 cannot have both pencil hardness and repeated bending resistance.

The invention provides a resin composition for providing a hard coating film with excellent pencil hardness and repeated bending resistance, a hard coating film with a hard coating layer containing a cured product of the resin composition, and polyorganosilsesquioxane.

Means for solving the technical problem

The present inventors have intensively studied and found that the above problems can be solved by the following means.

<1>

A resin composition comprising a polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond,

the polyorganosilsesquioxane has a hydrogen bond value of 3.0 or more and a side chain length of 14X 10^-10～19×10^-10m，

The hydrogen bond value is represented by the following formula (1), and the side chain length represents a length from the Si atom to the end of the side chain.

1, the number of hydrogen atoms capable of forming hydrogen bonds per 1 structural unit, x 1000

<2>

A resin composition comprising a polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond,

the polyorganosilsesquioxane has a hydrogen bond value of 3.0 or more and a crosslinkable group value of 4.5 to 6.0,

the hydrogen bond value is represented by the following formula (1), and the crosslinkable group value is represented by the following formula (5).

1, the number of hydrogen atoms capable of forming hydrogen bonds per 1 structural unit, x 1000

Value of crosslinkable group ═ 1 number of crosslinkable groups per 1 molecular weight of structural unit × 1000 … (5)

<3>

According to<1>Or<2>The resin composition, wherein, the polyorganosilsesquioxane has a hydrogen value of 3.0 or more and a side chain length of 14 x 10^-10～19×10^-10m, a crosslinkable group value of 4.5 to 6.0.

<4>

The resin composition according to any one of <1> to <3>, wherein the group containing a hydrogen atom capable of forming a hydrogen bond is at least one group selected from an amide group, a urethane group, a urea group and a hydroxyl group.

<5>

The resin composition according to any one of <1> to <4>, wherein the polyorganosilsesquioxane contains: a structural unit having a group containing a hydrogen atom capable of forming a hydrogen bond (S1); and a structural unit (S2) having a crosslinkable group which is different from the structural unit (S1).

<6>

The resin composition according to <5>, wherein the group containing a hydrogen atom capable of forming a hydrogen bond in the structural unit (S1) is at least one group selected from an amide group, a urethane group and a urea group.

<7>

The resin composition according to <5> or <6>, wherein the structural unit (S1) further has a crosslinkable group, and the crosslinkable group is a (meth) acryloyloxy group or a (meth) acrylamide group.

<8>

The resin composition according to any one of <5> to <7>, wherein the crosslinkable group of the structural unit (S2) is a (meth) acrylamide group.

<9>

The resin composition according to any one of claims 1 to 8, wherein the weight average molecular weight of the polyorganosilsesquioxane is 10000 to 1000000.

<10>

A hardcoat film having: a substrate; and a hard coat layer comprising a cured product of the resin composition described in any one of <1> to <9 >.

<11>

The hard coating film according to <10>, wherein the pencil hardness is 3H or more, and cracks are not generated when the 180 ° bending test is repeated 10 ten thousand times with the curvature radius of 2mm with the base material being inside.

<12>

A polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond, wherein,

hydrogen number of 3.0 or more and side chain length of 14X 10^-10～19×10^-10m，

The hydrogen bond value is represented by the following formula (1), and the side chain length represents a length from the Si atom to the end of the side chain.

1, the number of hydrogen atoms capable of forming hydrogen bonds per 1 structural unit, x 1000

<13>

A polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond, wherein,

a hydrogen bond value of 3.0 or more, a crosslinkable group value of 4.5 to 6.0,

the hydrogen bond value is represented by the following formula (1), and the crosslinkable group value is represented by the following formula (5).

Number of hydrogen atoms capable of forming hydrogen bonds in 1 structural unit/molecular weight of 1 structural unit × 1000 … … (1)

Value of crosslinkable group 1 number of crosslinkable groups/molecular weight of 1 structural unit × 1000

<14>

According to<12>Or<13>The poly-silicon timesA hemisiloxane, wherein the hydrogen bond value is 3.0 or more, and the side chain length is 14X 10^-10～19×10^-10m, a crosslinkable group value of 4.5 to 6.0.

Effects of the invention

The present invention can provide a resin composition for providing a hard coat film having excellent pencil hardness and excellent repeated bending resistance, a hard coat film having a hard coat layer containing a cured product of the resin composition, and a polyorganosilsesquioxane.

Detailed Description

Hereinafter, embodiments for carrying out the present invention will be described in detail, but the present invention is not limited to these embodiments. In the present specification, when numerical values indicate physical property values, characteristic values, and the like, the description of "(numerical value 1) to" (numerical value 2) "means" (numerical value 1) or more and (numerical value 2) or less). In the present specification, the expression "(meth) acrylate" means "at least one of acrylate and methacrylate". The same applies to "(meth) acrylic acid", "(meth) acryloyl", "(meth) acrylamide", "(meth) acryloyloxy", and the like.

[ resin composition ]

The present invention relates to a resin composition containing a polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond,

the polyorganosilsesquioxane has a hydrogen bond value of 3.0 or more and a side chain length of 14X 10^-10～19×10^-10m

The hydrogen bond value is represented by the following formula (1), and the side chain length represents a length from the Si atom to the end of the side chain.

(1) the number of hydrogen atoms capable of forming hydrogen bonds in 1 structural unit/molecular weight of 1 structural unit × 1000

The present invention also relates to a resin composition containing a polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond,

the polyorganosilsesquioxane has a hydrogen bond value of 3.0 or more and a crosslinkable group value of 4.5 to 6.0,

the hydrogen bond value is represented by the following formula (1), and the crosslinkable group value is represented by the following formula (5).

1, the number of hydrogen atoms capable of forming hydrogen bonds per 1 structural unit, x 1000

Value of crosslinkable group ═ 1 number of crosslinkable groups per 1 molecular weight of structural unit × 1000 … (5)

< polyorganosilsesquioxane (a1) having a group containing a hydrogen atom capable of forming a hydrogen bond >

A polyorganosilsesquioxane (a1) (also referred to as a "polyorganosilsesquioxane (a 1)") having a group containing a hydrogen atom capable of forming a hydrogen bond will be described.

(group containing hydrogen atom capable of forming hydrogen bond)

The polyorganosilsesquioxane (a1) has a group containing a hydrogen atom capable of forming a hydrogen bond. The hydrogen atom capable of forming a hydrogen bond is a hydrogen atom which is bonded to an atom having a large electronegativity through a covalent bond and is capable of forming a hydrogen bond with nitrogen, oxygen, or the like located in the vicinity.

The hydrogen atom-containing group of the polyorganosilsesquioxane (a1) may be a group containing a hydrogen atom capable of forming a hydrogen bond, which is generally known, and is preferably at least one group selected from the group consisting of an amide group, a urethane group, a urea group and a hydroxyl group, and more preferably at least one group selected from the group consisting of an amide group, a urethane group and a urea group.

In the present invention, an amide group represents a 2-valent linking group represented by-NH-C (═ O) -, a carbamate group represents a 2-valent linking group represented by-NH-C (═ O) -O-, and a urea group represents a 2-valent linking group represented by-NH-C (═ O) -NH-.

(Hydrogen bond value)

In the present invention, the hydrogen bond value indicates the density of hydrogen atoms capable of forming hydrogen bonds in the polyorganosilsesquioxane (a1), and is calculated from the following formula (1).

1, the number of hydrogen atoms capable of forming hydrogen bonds per 1 structural unit, x 1000

In addition, when the hydrogen atom capable of forming a hydrogen bond is an amide group, the number of hydrogen atoms capable of forming a hydrogen bond contained in the amide group is 1, the number is 1 in the case of a urethane group, the number is 2 in the case of a urea group, and the number is 1 in the case of a hydroxyl group.

The structural unit refers to a repeating unit of the polyorganosilsesquioxane (a1), and for example, when the polyorganosilsesquioxane (a1) is a polymer obtained by polymerizing only 1 monomer, the polyorganosilsesquioxane (a1) has 1 structural unit, and when the polyorganosilsesquioxane is a copolymer of 2 monomers, the structural unit is 2 structural units.

When the polyorganosilsesquioxane (a1) has 1 kind of structural unit, the hydrogen bond value of the polyorganosilsesquioxane (a1) is the hydrogen bond value of 1 structural unit calculated from the above formula (1).

When the polyorganosilsesquioxane (a1) has a plurality of structural units, the hydrogen bond value of the polyorganosilsesquioxane (a1) is defined as the sum of the hydrogen bond values calculated from the above formula (1) and the value obtained by multiplying the hydrogen bond value of each structural unit by the composition ratio (mol%) of each structural unit in the polyorganosilsesquioxane (a1) divided by 100 (average molar fraction).

Specifically, when the polyorganosilsesquioxane (a1) has 2 kinds of structural units (structural unit 1 and structural unit 2), the hydrogen bond value of the polyorganosilsesquioxane (a1) is calculated from the following formula (2A).

Hydrogen number value ═ H₁(hydrogen key value of structural Unit 1). times.W₁(composition ratio (mol%) of structural Unit 1)/100 + H₂(hydrogen key value of structural unit 2) × W₂(composition ratio (mol%) of the structural unit 2)/100

When the polyorganosilsesquioxane (a1) has the structural unit 1, the structural unit 2, or the structural unit X (X represents an integer of 3 or more), the hydrogen bond value of the polyorganosilsesquioxane (a1) is calculated by the following formula (2B).

Hydrogen number value ═ H₁(hydrogen key value of structural Unit 1). times.W₁(composition ratio (mol%) of structural Unit 1)/100 + H₂(hydrogen key value of structural unit 2) × W₂(composition ratio (mol%) of structural unit 2)/100 + … … H_X(hydrogen key value of structural unit X). times.W_x(composition ratio (mol%) of structural unit X)/100

In the present invention, the polyorganosilsesquioxane (a1) has a hydrogen atom capable of forming a hydrogen bond so that the hydrogen bond value becomes 3.0 or more. It is thus presumed that the density of hydrogen bonds formed by the polyorganosilsesquioxane (a1) can be increased, and the pencil hardness of the hard coat film can be increased. Further, it is assumed that the hydrogen bond can be reversibly cleaved and re-bonded, and even if the hydrogen bond is cleaved when the hard coat film is subjected to bending deformation, the hydrogen bond can be re-bonded after the deformation is eliminated, and therefore, a hard coat film resistant to bending deformation can be produced without lowering the pencil hardness.

The hydrogen value is 3.0 or more, preferably 4.0 or more, and more preferably 5.0 or more. The upper limit of the hydrogen bond value is not particularly limited, but is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less, from the viewpoint of the productivity of the polyorganosilsesquioxane.

(side chain Length)

In one embodiment of the present invention, the polyorganosilsesquioxane (a1) has a side chain length of 14X 10^-10～19×10^-10m is a side chain.

The side chain is a chain bonded to an Si atom in the polyorganosilsesquioxane (a1), and means a chain other than a structural portion composed of a siloxane bond (Si-O-Si).

The side chain length is a length from the Si atom to the end of the side chain, and is determined using "Winmostar" manufactured by X-Ability. In calculating the value of the side chain Length, the chemical structure from the Si atom to the end of the side chain is first inputted, then the most stable conformation is found by MOPAC (AM1), and then the numerical value of "Maximum Length Molecule" is found by executing "Van der Waals Molecular Surface" from the "Molecular weight area, volume" items.

When the polyorganosilsesquioxane (a1) has 1 type of side chain, that is, 1 type of structural unit, the side chain length calculated in 1 structural unit is set as the side chain length of the polyorganosilsesquioxane (a 1).

When the polyorganosilsesquioxane (a1) has a plurality of types of side chains, that is, has a plurality of types of structural units, the total (average molar fraction) of the side chain length calculated in each structural unit multiplied by the value obtained by dividing the composition ratio (% by mole) of each structural unit in the polyorganosilsesquioxane (a1) by 100 is defined as the side chain length of the polyorganosilsesquioxane (a 1).

Specifically, when the polyorganosilsesquioxane (a1) has 2 kinds of structural units (structural unit 1 and structural unit 2), the length of the side chain of the polyorganosilsesquioxane (a1) is calculated from the following formula (3A).

Length of side chain ═ L₁(side chain length of structural Unit 1) × W₁(composition ratio (mol%) of structural Unit 1)/100 + L₂(side chain length of structural Unit 2) × W₂(composition ratio (mol%) of the structural unit 2)/100

When the polyorganosilsesquioxane (a1) has the structural unit 1, the structural unit 2, or the structural unit … …, and X (X represents an integer of 3 or more), the length of the side chain of the polyorganosilsesquioxane (a1) is calculated by the following formula (3B).

Length of side chain ═ L₁(side chain length of structural Unit 1) × W₁(composition ratio (mol%) of structural Unit 1)/100 + L₂(side chain length of structural Unit 2) × W₂(composition ratio (mol%) of structural Unit 2)/100 + … L_X(side chain length of structural Unit X) × W_x(composition ratio (mol%) of structural unit X)/100

The longer the side chain, the more flexible the structure of the polyorganosilsesquioxane (a1) is, and the better the resistance of the hard coat film to repeated bending. On the other hand, the shorter the side chain, the harder the structure of the polyorganosilsesquioxane (a1), and the more improved the pencil hardness of the hard coat film.

In the present invention, the side chain length of the polyorganosilsesquioxane (a1) is 14 as a whole10^-10～19×10^{- 10}m, repeated bending resistance and pencil hardness.

The side chain length is preferably 15X 10^-10～18×10^-10m, more preferably 16X 10^-10～17×10^-10m。

The number of the element in the side chain is preferably 8 to 11, and more preferably 9 or 10.

The number of elements in the side chain indicates the number of elements constituting the main chain in the side chain, and does not include elements branched from the main chain. For example, the number of elements in isopropyl group is 7 in terms of the number of elements in 2, 3-acryloxypropyl group.

When the polyorganosilsesquioxane (a1) has 1 type of side chain, that is, 1 type of structural unit, the number of elements of the side chain in 1 type of structural unit is set to the number of elements of the side chain of the polyorganosilsesquioxane (a 1).

When the polyorganosilsesquioxane (a1) has a plurality of types of side chains, that is, has a plurality of types of structural units, the total (average molar fraction) of the number of elements of the side chain in each structural unit multiplied by the value obtained by dividing the composition ratio (mol%) of each structural unit in the polyorganosilsesquioxane (a1) by 100 is defined as the number of elements of the side chain of the polyorganosilsesquioxane (a 1).

Specifically, when the polyorganosilsesquioxane (a1) has 2 kinds of structural units (structural unit 1 and structural unit 2), the number of elements possessed by the side chain of the polyorganosilsesquioxane (a1) is calculated from the following formula (4A).

The number of elements contained in the side chain of the polyorganosilsesquioxane (a1) ═ N₁(number of elements of structural Unit 1) × W₁(composition ratio (mol%) of structural Unit 1)/100 + N₂(number of elements of structural Unit 2) × W₂(composition ratio (mol%) of the structural unit 2)/100

When the polyorganosilsesquioxane (a1) has the structural unit 1, the structural unit 2, or the structural unit … …, and X (X represents an integer of 3 or more), the number of elements included in the side chain of the polyorganosilsesquioxane (a1) is calculated from the following formula (4B).

PolyorganosilsesquioxaneThe number of elements contained in the side chain of the alkylene oxide (a1) ═ N₁(number of elements of structural Unit 1) × W₁(composition ratio (mol%) of structural Unit 1)/100 + N₂(number of elements of structural Unit 2) × W₂(composition ratio (mol%) of structural unit 2)/100_X(number of elements of structural unit X) × W_x(composition ratio (mol%) of structural unit X)/100

(crosslinkable group value)

In one embodiment of the present invention, the polyorganosilsesquioxane (a1) has a crosslinkable group.

The crosslinkable group is not particularly limited as long as it can form a covalent bond by reaction, and examples thereof include a radical polymerizable crosslinkable group and a cation polymerizable crosslinkable group.

As the radical polymerizable crosslinkable group, a generally known radical polymerizable crosslinkable group can be used. Examples of the radical polymerizable crosslinkable group include polymerizable unsaturated groups, specifically, vinyl groups, allyl groups, (meth) acryloyloxy groups, (meth) acrylamide groups, and the like, and (meth) acryloyloxy groups or (meth) acrylamide groups are preferable. Further, each of the above groups may have a substituent.

The (meth) acrylamide group exemplified as the crosslinkable group is a group containing an amide group, and also corresponds to a group containing a hydrogen atom capable of forming a hydrogen bond.

As the cationically polymerizable crosslinkable group, a conventionally known cationically polymerizable crosslinkable group can be used, and specific examples thereof include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoester groups, and vinyloxy groups. The cationically polymerizable group is preferably an alicyclic ether group or a vinyloxy group, and particularly preferably an epoxy group or an oxetane group. The epoxy group may be an alicyclic epoxy group (a group having a fused ring structure of an epoxy group and an alicyclic group). Further, each of the above groups may have a substituent.

The crosslinkable group of the polyorganosilsesquioxane (a1) is preferably a radical polymerizable crosslinkable group, and more preferably at least one group selected from a (meth) acryloyloxy group and a (meth) acrylamide group.

In the present invention, the crosslinkable group value represents the crosslinkable group density of the polyorganosilsesquioxane (a1), and is calculated from the following formula (5).

Value of crosslinkable group 1 number of crosslinkable groups/molecular weight of 1 structural unit × 1000

When the polyorganosilsesquioxane (a1) has 1 kind of structural unit, the crosslinkable group value calculated for 1 structural unit is defined as the crosslinkable group value of the polyorganosilsesquioxane (a 1).

When the polyorganosilsesquioxane (a1) has a plurality of structural units, the crosslinkable group value of the polyorganosilsesquioxane (a1) is determined as the sum of the values obtained by multiplying the crosslinkable group value of each structural unit calculated by the above formula (5) by the composition ratio (mol%) of each structural unit in the polyorganosilsesquioxane (a1) divided by 100 (average molar fraction).

Specifically, when the polyorganosilsesquioxane (a1) has 2 kinds of structural units (structural unit 1 and structural unit 2), the value of the crosslinkable group of the polyorganosilsesquioxane (a1) is calculated from the following formula (6A).

Value of crosslinkable group ═ C₁(crosslinkable group value of structural Unit 1) × W₁(composition ratio (mol%) of structural Unit 1)/100 + C₂(crosslinkable group value of structural Unit 2) × W₂(composition ratio (mol%) of structural Unit 2)/100 … … (6A)

When the polyorganosilsesquioxane (a1) has the structural unit 1 and the structural unit 2, the crosslinking group value of the polyorganosilsesquioxane (a1) is calculated from the following formula (6B).

Value of crosslinkable group ═ C₁(crosslinkable group value of structural Unit 1) × W₁(composition ratio (mol%) of structural Unit 1)/100 + C₂(crosslinkable group value of structural Unit 2) × W₂(composition ratio (mol%) of structural Unit 2)/100 + … … C_x(side chain length of structural Unit X) × W_X(Structure ofComposition ratio (mol%) of unit X)/100 … (6B)

The smaller the value of the crosslinkable group, the more flexible the structure of the polyorganosilsesquioxane (a1) is, and the better the resistance of the hard coat film to repeated bending. On the other hand, the harder the structure of the polyorganosilsesquioxane (a1) is as the value of the crosslinkable group is larger, and the pencil hardness of the hard coat film can be improved.

In the present invention, the repeated bending resistance and the pencil hardness can be achieved by setting the value of the crosslinkable group of the polyorganosilsesquioxane (a1) to 4.5 to 6.0.

The value of the crosslinkable group is preferably 4.8 to 5.8, more preferably 5.0 to 5.5.

In the polyorganosilsesquioxane (a1), the hydrogen value is more preferably 3.0 or more and the side chain length is 14X 10^-10～19×10^-10m, and the value of the crosslinkable group is 4.5 to 6.0.

The polyorganosilsesquioxane (a1) may be a polymer obtained by polymerizing only 1 kind of monomer, or may be a copolymer of 2 or more kinds of monomers. From the viewpoint of the productivity of the polyorganosilsesquioxane having a desired hydrogen value, side chain length, and crosslinkable group value, a copolymer of 2 or more monomers is preferable, and a copolymer of a monomer having a group containing a hydrogen atom capable of forming a hydrogen bond and a monomer having a crosslinkable group is more preferable.

The polyorganosilsesquioxane (a1) preferably contains: a structural unit having a group containing a hydrogen atom capable of forming a hydrogen bond (S1); and a structural unit (S2) having a crosslinkable group which is different from the structural unit (S1).

Structural units having a group containing a hydrogen atom capable of forming a hydrogen bond (S1) -

The structural unit (S1) has a group containing a hydrogen atom capable of forming a hydrogen bond. The group containing a hydrogen atom capable of forming a hydrogen bond in the structural unit (S1) is preferably at least one selected from the group consisting of an amide group, a urethane group, a urea group and a hydroxyl group, and more preferably at least one selected from the group consisting of an amide group, a urethane group and a urea group.

The structural unit (S1) may contain at least one hydrogen atom capable of forming a hydrogen bond, and preferably contains 1 or 2.

The structural unit (S1) preferably further has a crosslinkable group. The crosslinkable group is preferably a radical polymerizable crosslinkable group, more preferably a vinyl group, an allyl group, a (meth) acryloyloxy group or a (meth) acrylamide group, still more preferably a (meth) acryloyloxy group or a (meth) acrylamide group, and particularly preferably an acryloyloxy group or an acrylamide group.

The structural unit (S1) is preferably a structural unit represented by the following general formula (S1-1).

[ chemical formula 1]

In the general formula (S1-1),

L₁₁represents a substituted or unsubstituted alkylene group,

R₁₁represents a single bond, -NH-, -O-, -C (═ O) -or a 2-valent linking group obtained by combining these groups,

L₁₂represents a substituted or unsubstituted alkylene group,

Q₁₁represents a crosslinkable group.

Wherein the structural unit represented by the general formula (S1-1) has at least one group containing a hydrogen atom capable of forming a hydrogen bond.

"SiO" in the general formula (S1-1)_1.5"means a structural moiety composed of a siloxane bond (Si-O-Si) in the polyorganosilsesquioxane.

The polyorganosilsesquioxane is a network polymer or polyhedral cluster having a siloxane structural unit (silsesquioxane unit) derived from a hydrolyzable trifunctional silane compound, and can form a random structure, a ladder structure, a cage structure, or the like by siloxane bonding. In the present invention, "SiO_1.5The structural portion represented by "may have any of the above structures, but preferably includes a plurality of trapezoidal structures. By forming the trapezoidal structure, the deformation recovery property of the hard coat film can be maintained well. The trapezoidal structure can be formed by measuring FT-IR (Fourier)Fourier Transform basic spectrum) at 1020-1050 cm^-1The presence or absence of the absorption derived from the characteristic Si-O-Si stretching in the trapezoidal structure appearing in the vicinity was confirmed qualitatively.

In the general formula (S1-1), L₁₁The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, an isopropylidene group, a n-propylene group, a n-butylene group, a n-pentylene group, a n-hexylene group, and a n-decylenene group.

As L₁₁Examples of the substituent when the alkylene group has a substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group, a silyl group and the like.

L₁₁The alkyl group is preferably an unsubstituted linear alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or an n-propylene group, and still more preferably an n-propylene group.

In the general formula (S1-1), R₁₁Represents a single bond, -NH-, -O-, -C (═ O) -, or a 2-valent linking group obtained by combining these.

Examples of the 2-valent linking group obtained by combining — NH-, -O-, -C (═ O) -, NH-C (═ O) -NH-, — NH-C (═ O) -O-, — O-C (═ O) -NH-, — NH-C (═ O) -NH-, — O) -, and O-C (═ O) -, and the like. Represents a group represented by the general formula (S1-1) and L₁₁The bond of (A) represents a bond with L in the general formula (S1-1)₁₂The connecting bond of (1).

R₁₁Preferably, -NH-C (═ O) -NH-, — NH-C (═ O) -O-, — NH-C (═ O) -, or-O-, more preferably, -NH-C (═ O) -NH-, — NH-C (═ O) -O-, — or-NH-C (═ O) -.

In the general formula (S1-1), L₁₂The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, an isopropylidene group, a n-propylene group, a n-butylene group, a n-pentylene group, a n-hexylene group, and a n-decylenene group.

As L₁₂Examples of the substituent in the case where the alkylene group has a substituent include a hydroxyl group and a carboxyl groupAlkoxy groups, aryl groups, heteroaryl groups, halogen atoms, nitro groups, cyano groups, silyl groups, and the like.

L₁₂The alkylene group is preferably a linear alkylene group having 1 to 3 carbon atoms, more preferably a methylene group, an ethylene group, an n-propylene group or a 2-hydroxy-n-propylene group, and still more preferably a methylene group or an ethylene group.

In the general formula (S1-1), Q₁₁Represents a crosslinkable group. The crosslinkable group is preferably a radical polymerizable crosslinkable group, more preferably a vinyl group, an allyl group, a (meth) acryloyloxy group or a (meth) acrylamide group, still more preferably a (meth) acryloyloxy group or a (meth) acrylamide group, and particularly preferably an acryloyloxy group or an acrylamide group.

The structural unit represented by the general formula (S1-1) has at least one group containing a hydrogen atom capable of forming a hydrogen bond.

Examples of the group containing a hydrogen atom capable of forming a hydrogen bond include an amide group, a urethane group, a urea group, and a hydroxyl group.

It is preferable that 1 or 2 hydrogen atoms capable of forming a hydrogen bond are contained in the structural unit represented by the general formula (S1-1).

R in the formula (SI-1) of a hydrogen atom capable of forming a hydrogen bond₁₁Among them, the amide group, the urethane group, or the urea group is preferably contained.

The structural unit represented by the general formula (S1-1) is preferably a structural unit represented by the following general formula (S1-2).

[ chemical formula 2]

In the general formula (S1-2),

L₁₁represents a substituted or unsubstituted alkylene group,

r₁₁represents a single bond, -NH-or-O-,

L₁₂represents a substituted or unsubstituted alkylene group,

q₁₁represents-NH-or-O-,

q₁₂represents a hydrogen atom or a methyl group.

"SiO" in the general formula (S1-2)_1.5"means a structural moiety composed of a siloxane bond (Si-O-Si) in the polyorganosilsesquioxane.

In the general formula (S1-2), L₁₁Represents a substituted or unsubstituted alkylene group. L is₁₁And L in the general formula (S1-1)₁₁Synonymously, and the preferred examples are the same.

In the general formula (S1-2), L₁₂Represents a substituted or unsubstituted alkylene group. L is₁₂And L in the general formula (S1-1)₁₂Synonymously, and the preferred examples are the same.

q₁₂Represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

Structural units having crosslinkable groups (S2) -

The structural unit (S2) has a crosslinkable group. The crosslinkable group is preferably a radical polymerizable crosslinkable group, more preferably a vinyl group, an allyl group, a (meth) acryloyloxy group or a (meth) acrylamide group, still more preferably a (meth) acryloyloxy group or a (meth) acrylamide group, particularly preferably a (meth) acrylamide group, and most preferably an acrylamide group.

The structural unit (S2) is preferably a structural unit represented by the following general formula (S2-1).

[ chemical formula 3]

In the general formula (S1-2),

L₂₁represents a substituted or unsubstituted alkylene group,

Q₂₁represents a crosslinkable group.

"SiO" in the general formula (S2-1)_1.5"means a structural moiety composed of a siloxane bond (Si-O-Si) in the polyorganosilsesquioxane.

In the general formula (S2-1), L₂₁Represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, a methylmethylene group, and a dimethylene groupMethylene, ethylene, isopropylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-decylene, and the like.

As L₁₁Examples of the substituent when the alkylene group has a substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group, a silyl group and the like.

L₁₁The alkyl group is preferably an unsubstituted linear alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or an n-propylene group, and still more preferably an n-propylene group.

In the general formula (S2-1), Q₂₁Represents a crosslinkable group. The crosslinkable group is preferably a radical polymerizable crosslinkable group, more preferably a vinyl group, an allyl group, a (meth) acryloyloxy group or a (meth) acrylamide group, and still more preferably a (meth) acryloyloxy group or a (meth) acrylamide group.

The structural unit represented by the general formula (S2-1) is preferably a structural unit represented by the following general formula (S2-2).

[ chemical formula 4]

In the general formula (S2-2),

L₂₁represents a substituted or unsubstituted alkylene group,

q₂₁represents-NH-or-O-,

q₂₂represents a hydrogen atom or a methyl group.

"SiO" in the general formula (S2-2)_1.5"means a structural moiety composed of a siloxane bond (Si-O-Si) in the polyorganosilsesquioxane.

In the general formula (S2-2), L₂₁Represents a substituted or unsubstituted alkylene group. L is₂₁And L in the general formula (S2-1)₂₁Synonymously, and the preferred examples are the same.

q₂₁represents-NH-or-O-, preferably-NH-.

q₂₂Represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

The polyorganosilsesquioxane (a1) preferably contains a structural unit represented by the above general formula (S1-1) and a structural unit represented by the above general formula (S2-1), and more preferably contains a structural unit represented by the above general formula (S1-2) and a structural unit represented by the above general formula (S2-2).

When the polyorganosilsesquioxane (a1) has the structural unit (S1) and the structural unit (S2), the content molar ratio of the structural unit (S1) is preferably more than 1 mol% and 90 mol% or less, more preferably 15 mol% or more and 75 mol% or less, and still more preferably 35 mol% or more and 65 mol% or less with respect to all the structural units.

When the polyorganosilsesquioxane (a1) has the structural unit (S1) and the structural unit (S2), the content molar ratio of the structural unit (S2) is preferably 15 mol% or more and 85 mol% or less, more preferably 30 mol% or more and 80 mol% or less, and still more preferably 35 mol% or more and 65 mol% or less, with respect to all the structural units.

The polyorganosilsesquioxane (a1) may have a structural unit (S3) other than the structural unit (S1) and the structural unit (S2) within a range not affecting the effects of the present invention. The polyorganosilsesquioxane (a1) preferably contains the structural unit (S3) at a molar ratio of 10 mol% or less, more preferably 5 mol% or less, and further preferably does not contain the structural unit (S3) based on all the structural units.

When the polyorganosilsesquioxane (a1) is a polymer obtained by polymerizing only 1 monomer, the polyorganosilsesquioxane (a1) preferably has a structural unit (S1), more preferably has a structural unit represented by the above general formula (S1-1), and still more preferably has a structural unit represented by the above general formula (S1 — 2).

Specific examples of the polyorganosilsesquioxane (a1) are shown below, but the present invention is not limited to these. In the following structural formula, "SiO_1.5"denotes silsesquioxane units.

[ chemical formula 5]

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

From the viewpoint of improving the pencil hardness, the weight average molecular weight (Mw) of the polyorganosilsesquioxane (a1) in terms of polystyrene based on Gel Permeation Chromatography (GPC) standards is preferably 5000 to 1000000, more preferably 10000 to 1000000, and still more preferably 10000 to 100000.

The molecular weight dispersity (Mw/Mn) of the polyorganosilsesquioxane (a1) in terms of standard polystyrene based on GPC is, for example, 1.0 to 4.0, preferably 1.1 to 3.7, more preferably 1.2 to 3.0, and still more preferably 1.3 to 2.5. Mw represents a weight average molecular weight, and Mn represents a number average molecular weight.

The weight average molecular weight and the molecular weight dispersity of the polyorganosilsesquioxane (a1) were measured by the following apparatus and conditions.

A measuring device: trade name "LC-20 AD" (manufactured by SHIMADZU CORPORATION)

Column: shodex KF-801X 2, KF-802 and KF-803 (manufactured by SHOWA DENKO K.K.)

Measuring the temperature: 40 deg.C

Eluent: n-methylpyrrolidone (NMP) in a sample concentration of 0.1 to 0.2 mass%

Flow rate: 1 mL/min

A detector: UV-VIS detector (trade name "SPD-20A", manufactured by SHIMADZU CORPORATION)

Molecular weight: conversion to standard polystyrene

< method for producing polyorganosilsesquioxane (a1) >

The method for producing the polyorganosilsesquioxane (a1) is not particularly limited, and it can be produced by a known production method, for example, a method in which a hydrolyzable silane compound is hydrolyzed and condensed. As the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound having a group containing a hydrogen atom capable of forming a hydrogen bond (preferably, a compound represented by the following general formula (Sd 1-1)) and a hydrolyzable trifunctional silane compound having a crosslinkable group (preferably, a compound represented by the following general formula (Sd 2-1)) are preferably used.

The compound represented by the following general formula (Sd1-1) corresponds to the structural unit represented by the above general formula (S1-1), and the compound represented by the following general formula (Sd2-1) corresponds to the structural unit represented by the above general formula (S2-1).

[ chemical formula 12]

In the general formula (Sd1-1), X¹～X³Each independently represents an alkoxy group or a halogen atom, L₁₁Represents a substituted or unsubstituted alkylene group, R₁₁Represents a single bond-NH-, -O-, -C (-O) -, or a 2-valent linking group obtained by combining these groups, L₁₂Represents a substituted or unsubstituted alkylene group, Q₁₁Represents a crosslinkable group. Wherein the structural unit represented by the general formula (S1-1) has at least one group containing a hydrogen atom capable of forming a hydrogen bond.

In the general formula (Sd2-1), X⁴～X⁶Each independently represents an alkoxy group or a halogen atom, L₂₁Represents a substituted or unsubstituted alkylene group, Q₂1 represents a crosslinkable group.

L in the formula (Sd1-1)₁₁、R₁₁、L₁₂And Q₁₁Respectively with L in the general formula (S1-1)₁₁、R₁₁、L₁₂And Q₁₁Synonymously, the preferred ranges are also the same.

L in the formula (Sd2-1)₂₁And Q₂₁Respectively with L in the general formula (S2-1)₂₁And Q₂₁Synonymously, the preferred ranges are also the same.

In the general formula (Sd1-1) or the general formula (Sd2-1), X¹～X⁶Each independently represents an alkoxy group or a halogen atom.

Examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

As X¹～X⁶Preferably, the alkoxy group is a methoxy group or an ethoxy group. In addition, X¹～X⁶May be the same or different.

The amount and composition of the hydrolyzable silane compound may be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane (a 1).

The hydrolysis reaction and the condensation reaction of the hydrolyzable silane compound may be performed simultaneously or sequentially. When the above reactions are carried out sequentially, the order of carrying out the reactions is not particularly limited.

The hydrolysis reaction and condensation reaction of the hydrolyzable silane compound may be carried out in the presence or absence of a solvent, and preferably 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, methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; amides such as N, N-dimethylformamide, N-dimethylacetamide and the like; nitriles such as acetonitrile, propionitrile, benzonitrile; alcohols such as methanol, ethanol, isopropanol, butanol, and the like.

As the solvent, ketones or ethers are preferable. Further, 1 kind of solvent may be used alone, or 2 or more kinds may be used in combination.

The amount of the solvent used is not particularly limited, and may be usually in the range of 0 to 2000 parts by mass based on 100 parts by mass of the total amount of the hydrolyzable silane compound, and may be appropriately adjusted depending on the desired reaction time and the like.

The hydrolysis reaction and the condensation reaction of the hydrolyzable silane compound are preferably carried out in the presence of a catalyst and water. The catalyst may be an acid catalyst or a base catalyst.

The acid catalyst is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; a phosphate ester; carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid; solid acids such as activated clay; lewis acids such as ferric chloride, and the like.

The alkali catalyst is not particularly limited, and examples thereof include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate; organic acid salts (e.g., acetate salts) of alkali metals such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate; organic acid salts (e.g., acetate salts) of alkaline earth metals such as magnesium acetate; alkali metal alkoxides such as lithium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, and potassium tert-butoxide; alkali metal phenates such as sodium phenate; amines (tertiary amines, etc.) such as triethylamine, N-methylpiperidine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene; and nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2' -bipyridine and 1, 10-phenanthroline.

Further, 1 kind of catalyst may be used alone, or 2 or more kinds may be used in combination. The catalyst may be used in a state of being dissolved or dispersed in water, a solvent, or the like.

The amount of the catalyst used is not particularly limited, and may be appropriately adjusted within a range of 0.002 to 0.200 mol per 1 mol of the total amount of the hydrolyzable silane compound.

The amount of water used in the hydrolysis reaction and condensation reaction is not particularly limited, and may be appropriately adjusted within a range of 0.5 to 40 mol per 1 mol of the total amount of the hydrolyzable silane compound.

The method of adding water is not particularly limited, and the total amount of water used (the total amount used) may be added all at once or may be added sequentially. When the addition is carried out sequentially, the addition may be carried out continuously or intermittently.

The reaction temperature of the hydrolysis reaction and the condensation reaction is not particularly limited, and is, for example, 40 to 100 ℃ and preferably 45 to 80 ℃. The reaction time of the hydrolysis reaction and the condensation reaction is not particularly limited, and is, for example, 0.1 to 15 hours, preferably 1.5 to 10 hours. The hydrolysis reaction and the condensation reaction may be carried out under normal pressure, or under increased pressure or reduced pressure. The atmosphere in which the hydrolysis reaction and the condensation reaction are carried out may be, for example, any of a nitrogen atmosphere, an inert gas atmosphere such as an argon atmosphere, and the presence of oxygen such as air, but is preferably an inert gas atmosphere.

The polyorganosilsesquioxane (a1) can be obtained by hydrolysis and condensation of the hydrolyzable silane compound. The catalyst may be neutralized after the hydrolysis reaction and the condensation reaction are completed. Further, the polyorganosilsesquioxane (a1) may be isolated and purified by a separation method such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, or column chromatography, or a separation method using a combination thereof.

The polyorganosilsesquioxane (a1) may be used in a single amount of 1 type, or 2 or more types having different structures may be used in combination.

The hydrogen value, the side chain length, and the crosslinkable group value when 2 or more kinds of polyorganosilsesquioxane (a1) are mixed are calculated by multiplying the sum (mass average) of the values obtained by multiplying the respective values (hydrogen value, side chain length, and crosslinkable group value) by the blending ratio (mass ratio) as the value in the mixture.

The content of the polyorganosilsesquioxane (a1) in the resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more, based on the total solid content of the resin composition. The upper limit of the content of the polyorganosilsesquioxane (a1) in the resin composition is preferably 99.9% by mass or less, more preferably 98% by mass or less, and still more preferably 97% by mass or less, based on the total solid content of the resin composition.

In addition, the total solid content means all components except the solvent.

< polymerization initiator >

The resin composition in the present invention preferably contains a polymerization initiator.

The polyorganosiloxane (a1) used in the resin composition preferably contains a radical polymerization initiator if the crosslinkable group is a radical polymerizable crosslinkable group, and preferably contains a cationic polymerization initiator if the crosslinkable group is a cationic polymerizable crosslinkable group.

The polymerization initiator is preferably a radical polymerization initiator. The radical polymerization initiator may be a radical photopolymerization initiator or a radical thermal polymerization initiator, but is more preferably a radical photopolymerization initiator.

The polymerization initiator may be used alone in 1 kind, or 2 or more kinds different in structure may be used in combination.

As the radical photopolymerization initiator, any known radical photopolymerization initiator can be used without any limitation as long as it can generate radicals as active species by light irradiation. Specific examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholinyl (4 ═ thiomethylphenyl) propane ═ 1 ═ ketone, 2-benzyl-2 ═ dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone oligomer, and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } oligomer Acetophenones such as 2-methyl-propan-1-one; oxime esters such as 1, 2-octanedione, 1- [4- (phenylthio) -, 2 ═ benzoyl oxime ], ethanone, 1- [9 ═ ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (0-acetyloxime); benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyl-diphenyl sulfide, 3 ', 4, 4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2, 4, 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl ] phenylmethanesulfonamide, and (4-benzoylbenzyl) trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3, 4-dimethyl-9H-thioxanthone-9-one methylchloride (methochloride); acylphosphine oxides such as 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2, 4, 4-trimethyl-pentylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide; and the like. Further, as an auxiliary agent for the radical photopolymerization initiator, triethanolamine, triisopropanolamine, 4 '-dimethylaminobenzophenone (mikrolone), 4' -diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl (n-butoxy) 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, or the like may be used in combination.

The above radical photopolymerization initiator and auxiliary agent can be synthesized by a known method or can be obtained as a commercially available product.

The content of the polymerization initiator in the resin composition is not particularly limited, and is, for example, preferably 0.1 to 200 parts by mass, and more preferably 1 to 50 parts by mass, based on 100 parts by mass of the polyorganosilsesquioxane (a 1).

< solvent >

The resin composition in the present invention may contain a solvent.

The solvent is preferably an organic solvent, and 1 or 2 or more kinds of organic solvents can be mixed at an arbitrary ratio and used. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol, and isobutanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone; cellosolves such as ethyl cellosolve; aromatic compounds such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate, butyl acetate; diacetone alcohol, and the like.

The content of the solvent in the resin composition of the present invention can be appropriately adjusted within a range that can ensure coating suitability of the resin composition. For example, the amount of the organic solvent is 50 to 500 parts by mass, preferably 80 to 200 parts by mass, based on 100 parts by mass of the total solid content of the resin composition.

The resin composition is generally in a liquid form.

The concentration of the solid content in the resin composition is usually about 10 to 90 mass%, preferably about 20 to 80 mass%, and particularly preferably about 40 to 70 mass%.

< other additives >

The resin composition of the present invention may contain components other than those described above, and for example, inorganic fine particles, a dispersant, a leveling agent, an antifouling agent, an antistatic agent, an ultraviolet absorber, an antioxidant, and the like may be contained.

The resin composition used in the present invention can be prepared by mixing the above-described various components simultaneously or sequentially in any order. The production method is not particularly limited, and the production can be carried out using a known stirrer or the like.

[ hard coating film ]

The present invention relates to a hard coat film having: a substrate; and a hard coat layer comprising a cured product of the resin composition.

The hard coat film of the present invention preferably has the above hard coat layer on a substrate.

< substrate >

The transmittance of the substrate used in the hard coat film of the present invention in the visible light region is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.

(Polymer)

The substrate preferably comprises a polymer.

As the polymer, a polymer excellent in optical transparency, mechanical strength, thermal stability, and the like is preferable.

Examples of the polymer include a polycarbonate-based polymer, a polyester-based polymer such AS polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), and a styrene-based polymer such AS polystyrene or an acrylonitrile-styrene copolymer (AS resin). Further, there may be mentioned polyolefin such as polyethylene and polypropylene, norbornene resin, polyolefin polymer such as ethylene-propylene copolymer, (meth) acrylic polymer such as polymethyl methacrylate, (meth) acrylic polymer, vinyl chloride polymer, amide polymer such as nylon and aromatic polyamide, imide polymer, sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinylidene chloride polymer, vinyl alcohol polymer, vinyl butyral polymer, aryl ester polymer, polyoxymethylene polymer, epoxy polymer, cellulose polymer represented by triacetyl cellulose, copolymer of the above polymers, and polymer obtained by mixing the above polymers.

In particular, amide polymers such as aromatic polyamides and imide polymers have a large number of times of bending at break and a relatively high hardness as measured by an MIT tester in accordance with JIS (japanese industrial standards) P8115(2001), and thus can be preferably used as a substrate. For example, the aromatic polyamide described in example 1 of Japanese patent No. 5699454, the polyimide described in Japanese patent laid-open Nos. 2015-508345, 2016-521216 and WO2017/014287 can be preferably used as the substrate.

The amide polymer is preferably an aromatic polyamide (aromatic polyamide polymer).

The substrate preferably contains at least one polymer selected from the group consisting of an imide polymer and an aromatic polyamide polymer.

The base material may be a cured layer of an ultraviolet-curable or thermosetting resin such as an acrylic, urethane, acrylic urethane, epoxy, or silicone resin.

(softening material)

The base material may contain a material for further softening the polymer. The softening material is a compound that increases the number of times of breaking and bending, and as the softening material, a rubbery elastomer, a brittleness improver, a plasticizer, a slip ring polymer, or the like can be used.

Specifically, the softening raw material described in Japanese patent laid-open Nos. 2016-167043, paragraphs [0051] to [0114] can be preferably used.

The softening material may be mixed alone with the polymer or may be mixed in combination of a plurality of the softening materials, or may be used alone or in combination of a plurality of the softening materials as the base material without being mixed with the polymer.

The amount of the softening material to be mixed is not particularly limited, and the polymer having a sufficient number of bending times at break may be used alone as the base material of the film, or the softening material may be mixed, or the whole may be used as the softening material (100%) to have a sufficient number of bending times at break.

(other additives)

Various additives (for example, an ultraviolet absorber, a matting agent, an antioxidant, a peeling accelerator, a retardation (optical anisotropy) adjusting agent, and the like) may be added to the base material according to the use. They may be solid or oily. That is, the melting point or boiling point thereof is not particularly limited. The timing of adding the additive may be at any time during the step of producing the base material, or a step of adding the additive may be added during the raw material preparation step. The amount of each raw material added is not particularly limited as long as it functions.

As other additives, the additives described in paragraphs [0117] to [0122] of Japanese patent laid-open Nos. 2016-167043 can be preferably used.

The above additives may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(ultraviolet absorber)

Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, and benzoxazine compounds. The benzotriazole compound is a compound having a benzotriazole ring, and specific examples thereof include various benzotriazole-based ultraviolet absorbers described in paragraph 0033 of jp 2013-111835 a. The triazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based ultraviolet absorbers described in japanese patent application laid-open No. 2013-111835, paragraph 0033. As the benzoxazine compound, for example, the benzoxazine compound described in paragraph 0031 of japanese patent application laid-open No. 2014-209162 can be used. For example, the content of the ultraviolet absorber in the base material is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer contained in the base material, but is not particularly limited. Further, as for the ultraviolet absorber, refer to paragraph 0032 of Japanese patent laid-open publication No. 2013-111835. In the present invention, an ultraviolet absorber having high heat resistance and low volatility is preferable. Examples of such ultraviolet absorbers include UVSORB101 (manufactured by FUJIFILM Wako Pure Chemical Corporation), TINUVIN 360, TINUVIN 460, TINUVIN 1577 (manufactured by BASF Corporation), LA-F70, LA-31, LA-46 (manufactured by ADEKA Corporation), and the like.

From the viewpoint of transparency, the base material is preferably a softening material for the base material and the difference in refractive index between various additives and the polymer is small.

(substrate containing imide Polymer)

As the substrate, a substrate containing an imide-based polymer can be preferably used. In the present specification, an imide polymer refers to a polymer containing at least one or more repeating structural units represented by formula (PI), formula (a'), and formula (b). Among them, from the viewpoint of the strength and transparency of the film, it is preferable that the repeating structural unit represented by the formula (PI) is a main structural unit of the imide-based polymer. The repeating structural unit represented by the formula (PI) is preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 70 mol% or more, particularly preferably 90 mol% or more, and most preferably 98 mol% or more, based on all repeating structural units of the imide polymer.

[ chemical formula 13]

In the formula (PI), G represents a 4-valent organic group, and A represents a 2-valent organic group. G in the formula (a)²Represents a 3-valent organic group, A²Represents a 2-valent organic group. G in the formula (a')³Represents a 4-valent organic group, A³Represents a 2-valent organic group. G in the formula (b)⁴And A⁴Each represents a 2-valent organic group.

In the formula (PI), examples of the organic group of the 4-valent organic group represented by G (hereinafter, sometimes referred to as an organic group of G) include groups selected from the group consisting of acyclic aliphatic groups, cyclic aliphatic groups, and aromatic groups. The organic group of G is preferably a 4-valent cyclic aliphatic group or a 4-valent aromatic group from the viewpoint of transparency and flexibility of the substrate containing the imide polymer. Examples of the aromatic group include monocyclic aromatic groups, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups having 2 or more aromatic rings and connected to each other directly or through a linking group. From the viewpoint of transparency of the substrate and suppression of coloring, the organic group of G is preferably a cyclic aliphatic group, a cyclic aliphatic group having a fluorine-based substituent, a monocyclic aromatic group having a fluorine-based substituent, a condensed polycyclic aromatic group having a fluorine-based substituent, or a non-condensed polycyclic aromatic group having a fluorine-based substituent. In the present specification, a fluorine-based substituent means a group containing a fluorine atom. The fluorine-based substituent is preferably a fluorine group (fluorine atom, -F) or a perfluoroalkyl group, and more preferably a fluorine group or a trifluoromethyl group.

More specifically, the organic group of G is, for example, selected from a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroarylalkyl group, and a group having any 2 groups thereof (which may be the same) and which are connected to each other directly or through a linking group. Examples of the linking group include-O-, an alkylene group having 1 to 10 carbon atoms, -S0₂-, -CO-or-CO-NR- (R represents an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, or a hydrogen atom).

The number of carbon atoms of the 4-valent organic group represented by G is usually 2 to 32, preferably 4 to 15, more preferably 5 to 10, and further preferably 6 to 8. When the organic group of G is a cyclic aliphatic group or an aromatic group, at least one of carbon atoms constituting these groups may be substituted with a hetero atom. Examples of the heteroatom include O, N and S.

Specific examples of G include groups represented by formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), or formula (26) below. Wherein denotes a bond. Z in formula (26) represents a single bond, -O-, -CH₂-、-C(CH₃)₂-、-Ar-O-Ar-、-Ar-CH₂-Ar-、-Ar-C(CH₃)₂-Ar-or-Ar-SO₂-Ar-. Ar represents an aryl group having 6 to 20 carbon atoms, and may be a phenylene group, for example. At least one of the hydrogen atoms of these groups may be substituted with a fluorine-based substituent.

[ chemical formula 14]

In the formula (PI), examples of the organic group of the 2-valent organic group represented by a (hereinafter, sometimes referred to as an organic group of a) include groups selected from the group consisting of acyclic aliphatic groups, cyclic aliphatic groups, and aromatic groups. The 2-valent organic group represented by a is preferably selected from a 2-valent cyclic aliphatic group and a 2-valent aromatic group. Examples of the aromatic group include monocyclic aromatic groups, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups having 2 or more aromatic rings and connected to each other directly or through a linking group. From the viewpoint of transparency of the substrate and suppression of coloring, it is preferable to introduce a fluorine-based substituent into the organic group of a.

More specifically, the organic group of a is selected from, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroarylalkyl group, and a group having any 2 groups thereof (which may be the same) and which are connected to each other directly or through a linking group. The heteroatom includes O, N or S, and the linking group includes-O-, an alkylene group having 1 to 10 carbon atoms, and-SO₂-, -CO-or-CO-NR- (R includes an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, etc., or a hydrogen atom).

The number of carbon atoms of the 2-valent organic group represented by A is usually 2 to 40, preferably 5 to 32, more preferably 12 to 28, and further preferably 24 to 27.

Specific examples of A include the following groups represented by formula (30), formula (31), formula (32), formula (33) or formula (34). Wherein denotes a bond. Z¹～Z³Each independently represents a single bond, -O-, -CH₂-、-C(CH₃)₂-、-SO₂-, -CO-or-CO-NR- (R represents an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, or a hydrogen atom). In the following groups, Z¹And Z²And Z²And Z³Preferably in the meta or para position, respectively, with respect to the rings. And, Z¹Single bond to terminal, Z²A single bond to the terminal, and Z³The single bond to the terminal is preferably in the meta or para position, respectively. In 1 instance of A, Z¹And Z³is-O-, and Z²is-CH₂-、-C(CH₃)₂-or-SO₂-. 1 or 2 or more of the hydrogen atoms of these groups may be substituted with a fluorine-based substituent.

[ chemical formula 15]

At least one of the hydrogen atoms constituting at least one of A and G may be substituted with at least one functional group selected from the group consisting of a fluorine-based substituent, a hydroxyl group, a sulfone group, an alkyl group having 1 to 10 carbon atoms, and the like. When the organic group of a and the organic group of G are each a cyclic aliphatic group or an aromatic group, at least one of a and G preferably has a fluorine-based substituent, and more preferably both a and G have a fluorine-based substituent.

G in the formula (a)²Is a 3-valent organic group. The organic group may be selected from the same groups as those of G in the formula (PI), except that it is a 3-valent group. As G²Specific examples of G include those in which 1 of the 4 bonds in the groups represented by the formulae (20) to (26) are replaced by a hydrogen atom. A in the formula (a)²May be selected from the same groups as A in formula (PI).

G in the formula (a')³May be selected from the same groups as G in formula (PI). A in the formula (a')³May be selected from the same groups as A in the formula (PI)。

G in the formula (b)⁴Is a 2-valent organic group. The organic group may be selected from the same groups as those of G in the formula (PI), except that it is a 2-valent group. As G⁴Specific examples of G include those in which 2 of the 4 bonds in the groups represented by the formulae (20) to (26) are replaced by hydrogen atoms. A in the formula (b)⁴May be selected from the same groups as A in formula (PI).

The imide polymer contained in the imide polymer-containing base material may be a condensation-type polymer obtained by polycondensing at least one of diamines, tetracarboxylic acid compounds (including tetracarboxylic acid compound analogs such as acid chloride compounds and tetracarboxylic dianhydride), and tricarboxylic acid compounds (including tricarboxylic acid compound analogs such as acid chloride compounds and tricarboxylic acid anhydride). It is also possible to polycondense dicarboxylic acid compounds (including acid chloride compounds and the like). The repeating structural unit represented by formula (PI) or formula (a') is generally derived from diamines and tetracarboxylic acid compounds. The repeating structural unit represented by formula (a) is generally derived from diamine and tricarboxylic acid compounds. The repeating structural unit represented by the formula (b) is generally derived from diamines and dicarboxylic acid compounds.

Examples of the tetracarboxylic acid compound include aromatic tetracarboxylic acid compounds, alicyclic tetracarboxylic acid compounds, and acyclic aliphatic tetracarboxylic acid compounds. These may be used in combination of 2 or more. The tetracarboxylic acid compound is preferably a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and acyclic aliphatic tetracarboxylic dianhydride.

The tetracarboxylic acid compound is preferably an alicyclic tetracarboxylic acid compound, an aromatic tetracarboxylic acid compound, or the like, from the viewpoint of solubility of the imide polymer in a solvent, and transparency and flexibility when forming a substrate. The tetracarboxylic acid compound is preferably selected from alicyclic tetracarboxylic acid compounds having a fluorine-based substituent and aromatic tetracarboxylic acid compounds having a fluorine-based substituent, and more preferably alicyclic tetracarboxylic acid compounds having a fluorine-based substituent, from the viewpoint of transparency of the substrate containing the imide-based polymer and suppression of coloration.

Examples of the tricarboxylic acid compound include aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids, and acid chloride compounds and acid anhydrides similar thereto. The tricarboxylic acid compound is preferably selected from aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids, and acyl chloride compounds similar thereto. The tricarboxylic acid compound may be used in combination of 2 or more.

The tricarboxylic acid compound is preferably an alicyclic tricarboxylic acid compound or an aromatic tricarboxylic acid compound from the viewpoint of solubility of the imide polymer in a solvent, and transparency and flexibility when forming a substrate containing the imide polymer. From the viewpoint of transparency of the substrate containing the imide polymer and suppression of coloring, the tricarboxylic acid compound is more preferably an alicyclic tricarboxylic acid compound having a fluorine-based substituent or an aromatic tricarboxylic acid compound having a fluorine-based substituent.

Examples of the dicarboxylic acid compound include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, and acid chloride compounds and acid anhydrides similar thereto. The dicarboxylic acid compound is preferably selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, and acyl chloride compounds similar thereto. The dicarboxylic acid compound may be used in combination of 2 or more.

The dicarboxylic acid compound is preferably an alicyclic dicarboxylic acid compound or an aromatic dicarboxylic acid compound from the viewpoints of solubility of the imide polymer in a solvent, and transparency and flexibility when forming a substrate containing the imide polymer. The dicarboxylic acid compound is more preferably an alicyclic dicarboxylic acid compound having a fluorine-based substituent or an aromatic dicarboxylic acid compound having a fluorine-based substituent from the viewpoint of transparency of the substrate containing the imide-based polymer and suppression of coloration.

The diamines include aromatic diamines, alicyclic diamines, and aliphatic diamines, and 2 or more of these diamines may be used in combination. The diamine is preferably selected from alicyclic diamines and aromatic diamines having a fluorine-based substituent, from the viewpoint of solubility of the imide-based polymer in a solvent and transparency and flexibility in forming a substrate containing the imide-based polymer.

When such an imide-based polymer is used, a substrate having particularly excellent flexibility, high light transmittance (for example, 85% or more, preferably 88% or more with respect to 550nm light), low yellowness (YI value, 5 or less, preferably 3 or less), and low haze (1.5% or less, preferably 1.0% or less) can be easily obtained.

The imide-based polymer may be a copolymer containing different plural kinds of the above-mentioned repeating structural units. The weight average molecular weight of the polyimide polymer is usually 10,000 to 500,000. The weight average molecular weight of the imide polymer is preferably 50,000 to 500,000, more preferably 70,000 to 400,000. The weight average molecular weight is a standard polystyrene-equivalent molecular weight measured by Gel Permeation Chromatography (GPC). If the weight average molecular weight of the imide polymer is large, high bendability tends to be easily obtained, but if the weight average molecular weight of the imide polymer is large, varnish viscosity tends to be high, and processability tends to be low.

The imide-based polymer may contain a halogen atom such as a fluorine atom which can be introduced by the fluorine-based substituent or the like. When the polyimide-based polymer contains a halogen atom, the elastic modulus of the substrate containing the imide-based polymer can be increased and the yellowness can be reduced. This can suppress scratches, wrinkles, and the like generated on the hard coat film, and can improve the transparency of the substrate containing the imide polymer. The halogen atom is preferably a fluorine atom. The content of the halogen atom in the polyimide polymer is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, based on the mass of the polyimide polymer.

The imide-based polymer-containing substrate may contain 1 or 2 or more kinds of ultraviolet absorbers. The ultraviolet absorber may be appropriately selected from ultraviolet absorbers generally used as ultraviolet absorbers in the field of resin materials. The ultraviolet absorber may contain a compound that absorbs light having a wavelength of 400nm or less. Examples of the ultraviolet absorber that can be appropriately combined with the imide polymer include at least one compound selected from the group consisting of benzophenone compounds, salicylate compounds, benzotriazole compounds, and triazine compounds.

In the present specification, the term "system compound" refers to a derivative of a compound to which the "system compound" is attached. For example, the "benzophenone-based compound" refers to a compound having benzophenone as a parent skeleton and a substituent bonded to benzophenone.

The content of the ultraviolet absorber is usually 1 mass% or more, preferably 2 mass% or more, more preferably 3 mass% or more, and usually 10 mass% or less, preferably 8 mass% or less, more preferably 6 mass% or less, with respect to the total mass of the substrate. By containing the ultraviolet absorber in such an amount, the weather resistance of the substrate can be improved.

The imide-based polymer-containing substrate may further contain an inorganic material such as inorganic particles. The inorganic material is preferably a silicon material containing silicon atoms. By incorporating an inorganic material such as a silicon material into the imide polymer-containing substrate, the tensile elastic modulus of the imide polymer-containing substrate can be easily set to 4.0GPa or more. However, the method of controlling the tensile elastic modulus of the imide polymer-containing base material is not limited to the blending of the inorganic material.

Examples of the silicon material containing a silicon atom include silicon dioxide particles, quaternary alkoxysilane such as tetraethyl orthosilicate (TEOS), and a silicon compound such as a silsesquioxane derivative. Among these silicon materials, silica particles are preferable from the viewpoint of transparency and flexibility of the substrate containing an imide polymer.

The average primary particle diameter of the silica particles is usually 100nm or less. When the average primary particle diameter of the silica particles is 100nm or less, the transparency tends to be improved.

The average primary particle diameter of the silica particles in the imide polymer-containing base material can be determined by Transmission Electron Microscope (TEM) observation. The primary particle diameter of the silica particles may be set to an oriented diameter measured by a Transmission Electron Microscope (TEM). The average primary particle size can be determined as an average value of 10-point primary particle sizes measured by TEM observation. The particle distribution of the silica particles before forming the imide-based polymer-containing substrate can be determined by a commercially available laser diffraction particle size distribution meter.

In the imide polymer-containing substrate, the total mixing ratio of the imide polymer and the inorganic material is 10, and the mass ratio is preferably 1: 9 to 10: 0, more preferably 3: 7 to 10: 0, further preferably 3: 7 to 8: 2, and further preferably 3: 7 to 7: 3. The proportion of the inorganic material to the total mass of the imide-based polymer and the inorganic material is usually 20 mass% or more, preferably 30 mass% or more, usually 90 mass% or less, preferably 70 mass% or less. When the mixing ratio of the imide polymer and the inorganic material (silicon material) is in the above range, the transparency and mechanical strength of the substrate containing the imide polymer tend to be improved. Further, the tensile elastic modulus of the substrate containing the imide polymer can be easily set to 4.0GPa or more.

The substrate containing an imide polymer may further contain a component other than the imide polymer and the inorganic material within a range where transparency and flexibility are not significantly impaired. Examples of the component other than the imide-based polymer and the inorganic material include an antioxidant, a release agent, a stabilizer, a coloring agent such as a bluing agent, a flame retardant, a lubricant, a thickener, and a leveling agent. The ratio of the imide-based polymer to the components other than the inorganic material is preferably more than 0% and 20% by mass or less, and more preferably more than 0% and 10% by mass or less, based on the mass of the substrate.

When the substrate containing an imide polymer contains an imide polymer and a silicon material, the atomic ratio of silicon atoms to nitrogen atoms, i.e., Si/N, in at least one surface is preferably 8 or more. The atomic ratio Si/N is a value calculated from the amount of silicon atoms and the amount of nitrogen atoms present, which are obtained by evaluating the composition of a substrate containing an imide polymer by X-ray Photoelectron Spectroscopy (XPS).

By setting the Si/N of at least one surface of the base material containing an imide polymer to 8 or more, sufficient adhesion to the hard coat layer can be obtained. From the viewpoint of adhesion, Si/N is more preferably 9 or more, further preferably 10 or more, preferably 50 or less, and more preferably 40 or less.

(thickness of substrate)

The substrate is preferably in the form of a film.

The thickness of the substrate is more preferably 100 μm or less, still more preferably 80 μm or less, and most preferably 50 μm or less. When the thickness of the substrate is reduced, the difference in curvature between the front surface and the back surface at the time of bending is reduced, cracks are less likely to occur, and the substrate is not broken even when bent many times. On the other hand, the thickness of the substrate is preferably 3 μm or more, more preferably 5 μm or more, and most preferably 15 μm or more, from the viewpoint of ease of handling the substrate.

(method of producing substrate)

The substrate may be formed into a film by thermally melting a thermoplastic polymer, or may be formed into a film from a solution in which a polymer is uniformly dissolved by solution casting. In the case of film formation by hot melting, the softening material and various additives may be added during hot melting. On the other hand, when a substrate is produced by the solution film-forming method, a softening material and various additives described in the respective production steps may be added to a polymer solution (hereinafter, also referred to as a dope). The timing of the addition may be at any time during the dope producing step, or a step of adding an additive during the final producing step of the dope producing step may be added.

The coating may also be heated in order to dry and/or bake the coating. The heating temperature of the coating film is usually 50 to 350 ℃. The heating of the coating film may be performed under an inert atmosphere or under reduced pressure. By heating the coating film, the solvent can be evaporated and removed. The substrate can also be formed by a method comprising a step of drying the coating film at 50 to 150 ℃ and a step of baking the dried coating film at 180 to 350 ℃.

At least one side of the substrate may be subjected to a surface treatment.

< hard coating layer >

The hard coat film of the present invention has a hard coat layer containing a cured product of the resin composition.

The hard coat layer is preferably formed on at least one side of the substrate.

When the hard coating film of the present invention has a scratch resistant layer described later, it is preferable to have at least 1 hard coating layer between the substrate and the scratch resistant layer.

(cured product of resin composition)

The hard coat layer of the hard coat film of the present invention comprises a cured product of a resin composition containing a polyorganosilsesquioxane (a1), preferably a cured product of a resin composition containing a polyorganosilsesquioxane (a1) and a polymerization initiator.

The cured product of the resin composition preferably contains a cured product in which at least the crosslinkable groups of the polyorganosilsesquioxane (a1) are bonded by polymerization.

The content of the cured product of the resin composition in the hard coat layer of the hard coat film of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more.

(film thickness of hard coat layer)

The film thickness of the hard coat layer is not particularly limited, but is preferably 0.5 to 30 μm, more preferably 1 to 25 μm, and still more preferably 2 to 20 μm.

The film thickness of the hard coat layer was calculated by observing the cross section of the hard coat film with an optical microscope. The cross-sectional sample can be produced by a Microtome method using an Ultra Microtome (Ultra Microtome) cross-sectional cutting device, a cross-sectional processing method using a Focused Ion Beam (FIB) device, or the like.

< scratch-resistant layer >

The hard coat film of the present invention also preferably has a scratch-resistant layer.

When the hard coating film of the present invention has a scratch resistant layer, it is preferable to have at least 1 scratch resistant layer on the surface of the hard coating layer on the side opposite to the substrate.

The scratch-resistant layer of the hard coating film of the present invention preferably comprises a cured product of the scratch-resistant layer forming composition containing the radical polymerizable compound (c 1).

(radically polymerizable Compound (c1))

The radical polymerizable compound (c1) (also referred to as "compound (c 1)") will be described.

The compound (c1) is a compound having a radical polymerizable group.

The radical polymerizable group in the compound (c1) is not particularly limited, and a generally known radical polymerizable group can be used. Examples of the radical polymerizable group include polymerizable unsaturated groups, specifically (meth) acryloyl groups, vinyl groups, and allyl groups, and (meth) acryloyl groups are preferable. Further, each of the above groups may have a substituent.

The compound (c1) is preferably a compound having 2 or more (meth) acryloyl groups in 1 molecule, and more preferably a compound having 3 or more (meth) acryloyl groups in 1 molecule.

The molecular weight of the compound (c1) is not particularly limited, and it may be a monomer, an oligomer or a polymer.

Specific examples of the compound (c1) are shown below, but the present invention is not limited to these.

Examples of the compound having 2 (meth) acryloyl groups in 1 molecule include neopentyl glycol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyl di (meth) acrylate.

Examples of the compound having 3 or more (meth) acryloyl groups in 1 molecule include esters of a polyhydric alcohol and (meth) acrylic acid. Specific examples thereof include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexaacrylate, and the like, but pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and mixtures thereof are preferable from the viewpoint of high crosslinking.

Only 1 kind of compound (c1) may be used, or 2 or more kinds of compounds having different structures may be used in combination.

The content of the compound (c1) in the scratch-resistant layer-forming composition is preferably 80 mass% or more, more preferably 85 mass% or more, and still more preferably 90 mass% or more, relative to the total solid content in the scratch-resistant layer-forming composition.

(radical polymerization initiator)

The scratch-resistant layer-forming composition of the present invention preferably contains a radical polymerization initiator.

The radical polymerization initiator may be used alone in 1 kind, or may be used in combination with 2 or more kinds different in structure. The radical polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.

The content of the radical polymerization initiator in the scratch-resistant layer-forming composition is not particularly limited, and is, for example, preferably 0.1 to 200 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of the compound (c 1).

(solvent)

The scratch-resistant layer-forming composition of the present invention may contain a solvent.

The solvent is the same as the solvent that the resin composition may contain.

The content of the solvent in the scratch-resistant layer-forming composition of the present invention can be appropriately adjusted within a range that can ensure coating suitability of the scratch-resistant layer-forming composition. For example, the amount of the scratch-resistant layer forming composition may be 50 to 500 parts by mass, and preferably 80 to 200 parts by mass, based on 100 parts by mass of the total solid content of the scratch-resistant layer forming composition.

The scratch-resistant layer-forming composition is usually in a liquid form.

The concentration of the solid component in the scratch-resistant layer-forming composition is usually about 10 to 90 mass%, preferably about 20 to 80 mass%, and particularly preferably about 40 to 70 mass%.

(other additives)

The scratch-resistant layer-forming composition may contain components other than those described above, and may contain, for example, inorganic particles, a leveling agent, an antifouling agent, an antistatic agent, a lubricant, a solvent, and the like.

The following fluorine-containing compound is particularly preferably contained as the lubricant.

[ fluorine-containing Compound ]

The fluorine-containing compound may be any of a monomer, an oligomer, and a polymer. The fluorine-containing compound preferably has a substituent which contributes to bond formation with the compound (c1) in the scratch-resistant layer or contributes to compatibility. The substituents may be the same or different, and preferably there are a plurality of such substituents.

The substituent is preferably a polymerizable group as long as it is a polymerizable reactive group exhibiting any of radical polymerizability, cationic polymerizability, anionic polymerizability, condensation polymerizability, and addition polymerizability, and preferable examples of the substituent include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a cinnamoyl group, an epoxy group, an oxetanyl group, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, and an amino group. Among them, radical polymerizable groups are preferable, and among them, acryloyl and methacryloyl are particularly preferable.

The fluorine-containing compound may be a polymer or oligomer with a compound containing no fluorine atom.

The fluorine-containing compound is preferably a fluorine-containing compound represented by the following general formula (F).

General formula (F): (R)^f)-[(W)-(R^A)_nf]_mf

(in the formula, R^fRepresents a (per) fluoroalkyl group or a (per) fluoropolyether group, W represents a single bond or a linking group, and RA represents a polymerizable unsaturated group. nf represents an integer of 1 to 3And (4) counting. mf represents an integer of 1 to 3. )

In the general formula (F), R^ARepresents a polymerizable unsaturated group. The polymerizable unsaturated group is preferably a group having an unsaturated bond capable of causing a radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays or electron beams (that is, a radical polymerizable group), and examples thereof include a (meth) acryloyl group, a (meth) acryloyloxy group, a vinyl group, an allyl group, and the like, and it is preferable to use a (meth) acryloyl group, a (meth) acryloyloxy group, and a group in which any hydrogen atom in these groups is substituted with a fluorine atom.

In the general formula (F), R^fRepresents a (per) fluoroalkyl group or a (per) fluoropolyether group.

Here, the (per) fluoroalkyl group represents at least one of a fluoroalkyl group and a perfluoroalkyl group, and the (per) fluoropolyether group represents at least one of a fluoropolyether group and a perfluoropolyether group. From the viewpoint of scratch resistance, R^fThe higher the fluorine content in (2), the better.

The (per) fluoroalkyl group preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms.

The (per) fluoroalkyl group may be a linear structure (e.g., -CF)₂CF₃、-CH₂(CF₂)₄H、-CH₂(CF₂)₈CF₃、-CH₂CH₂(CF₂)₄H) May be a branched structure (e.g., -CH (CF)₃)₂、-CH₂CF(CF₃)₂、-CH(CH₃)CF₂CF₃、-CH(CH₃)(CF₂)₅CF₂H) And may be an alicyclic structure (preferably a 5-or 6-membered ring, such as perfluorocyclohexyl and perfluorocyclopentyl, and an alkyl group substituted with these groups).

The (per) fluoropolyether group means a group in which the (per) fluoroalkyl group has an ether bond and may have a valence of 1 or 2 or more. Examples of the fluoropolyether group include-CH₂OCH₂CF₂CF₃、-CH₂CH₂OCH₂C₄F₈H、-CH₂CH₂OCH₂CH₂C₈F₁₇、-CH₂CH₂OCF₂CF₂OCF₂CF₂H. And a fluorocycloalkyl group having 4 to 20 carbon atoms and having 4 or more fluorine atoms. Further, the perfluoropolyether group includes, for example, - (CF)₂O)_pf-(CF₂CF₂O)_qf-、-[CF(CF₃)CF₂O]_pf-[CF(CF₃)]_qf-、-(CF₂CF₂CF₂O)_pf-、-(CF₂CF₂O)_pf-and the like.

Pf and qf each independently represent an integer of 0 to 20. Wherein pf + qf is an integer of 1 or more.

The total of Pf and qf is preferably 1 to 83, more preferably 1 to 43, and further preferably 5 to 23.

The fluorine-containing compound is particularly preferably one having a structure represented by- (CF) in view of excellent scratch resistance₂O)_pf-(CF₂CF₂O)_qf-a perfluoropolyether group represented by.

In the present invention, the fluorine-containing compound preferably has a perfluoropolyether group and a plurality of polymerizable unsaturated groups in one molecule.

In the general formula (F), W represents a linking group. Examples of W include alkylene, arylene, and heteroalkylene groups, and a linking group formed by combining these groups. These linking groups may have an oxygen group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, or the like, or a functional group obtained by combining these groups.

W is preferably an ethylene group, and more preferably an ethylene group bonded to a carbonylimino group.

The fluorine atom content of the fluorine-containing compound is not particularly limited, but is preferably 20% by mass or more, more preferably 30 to 70% by mass, and still more preferably 40 to 70% by mass.

Examples of preferred fluorine-containing compounds include, but are not limited to, R-2020, M-2020, R-3833, M-3833 and OPTOOL DAC (trade name) manufactured by Daikin Industries, Ltd., Megafac F-171, F-172, F-179A, RS-78, RS-90, DEFENSA MCF-300 and MCF-323 (trade name) manufactured by DIC Corporation.

In the general formula (F), the product of nf and mf is preferably (nf × mf)2 or more, and more preferably 4 or more, from the viewpoint of scratch resistance.

The weight average molecular weight (Mw) of the fluorochemical having a polymerizable unsaturated group can be measured using size exclusion chromatography, such as Gel Permeation Chromatography (GPC).

The Mw of the fluorine-containing compound used in the present invention is preferably 400 or more and less than 50000, more preferably 400 or more and less than 30000, and further preferably 400 or more and less than 25000.

The content of the fluorine-containing compound is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, even more preferably 0.5 to 5% by mass, and particularly preferably 0.5 to 2% by mass, based on the total solid content in the scratch-resistant layer-forming composition.

The scratch-resistant layer-forming composition used in the present invention can be prepared by mixing the above-described various components simultaneously or sequentially in any order. The production method is not particularly limited, and the production can be carried out using a known stirrer or the like.

(cured product of scratch-resistant layer-forming composition)

The scratch-resistant layer of the hard coating film of the present invention preferably comprises a cured product of the scratch-resistant layer-forming composition containing the compound (c1), and more preferably comprises a cured product of the scratch-resistant layer-forming composition containing the compound (c1) and a radical polymerization initiator.

The cured product of the scratch-resistant layer-forming composition preferably contains at least a radical polymerizable group of the compound (c1) and is obtained by polymerization reaction.

The content of the cured product of the scratch-resistant layer-forming composition in the scratch-resistant layer of the hard coating film of the present invention is preferably 60 mass% or more, more preferably 70 mass% or more, and still more preferably 80 mass% or more, based on the total mass of the scratch-resistant layer.

(film thickness of scratch-resistant layer)

The thickness of the scratch-resistant layer is preferably less than 3.0. mu.m, more preferably 0.1 to 2.0. mu.m, and still more preferably 0.1 to 1.0. mu.m, from the viewpoint of repeated bending resistance.

< Pencil hardness >

The hard coat film of the present invention has excellent pencil hardness.

The hard coat film of the present invention preferably has a pencil hardness of 3H or more, more preferably 4H or more.

The pencil hardness can be evaluated in accordance with JIS (Japanese Industrial Standards, JIS) K5400.

< resistance to repeated flexing >

The hard coat film of the present invention has excellent repeated bending resistance.

The hard coat film of the present invention preferably has no cracks when the 180 ° bending test is repeated 10 ten thousand times with a curvature radius of 2mm with the substrate as the inner side.

The repeated bending resistance is specifically measured as follows.

A sample film having a width of 15mm and a length of 150mm was cut out from the hard coat film, and the film was allowed to stand at a temperature of 25 ℃ and a relative humidity of 65% for 1 hour or more. Thereafter, a repeated bending resistance test was performed using a 180 ° folding resistance tester (model IMC-0755 manufactured by Imoto mechanical co., LTD) with the substrate as the inner side. In the above-described testing machine, the test was repeated 1 time by the operation of bending the sample film at the central portion in the longitudinal direction at a bending angle of 180 ° along the curved surface of a rod (cylinder) having a diameter of 4mm and then restoring (spreading the sample film). It was visually evaluated whether or not cracks were generated when the 180 ° bending test was repeated.

The hard coating film having the substrate and the hard coating layer in this order and containing the cured product of the resin composition containing the polyorganosilsesquioxane (a1) as the hard coating layer can be excellent in the repeated bending resistance and pencil hardness.

The hard coat film is preferably a hard coat film which has a pencil hardness of 3H or more and does not crack when the 180 DEG bending test is repeated 10 ten thousand times with the substrate as the inner side and a curvature radius of 2 mm.

< method for producing hard coating film >

The method for producing a hard coat film of the present invention will be explained.

The method for producing a hard coat film of the present invention preferably includes the following steps (I) and (II). When the hard coat film has a scratch-resistant layer, the production method preferably further includes the following steps (III) and (IV).

(I) A step of forming a hard coat coating film by coating a resin composition containing a polyorganosilsesquioxane (a1) on a substrate

(II) a step of forming a hard coat layer by curing the hard coat layer coating film

(III) coating the hard coat layer with a scratch-resistant layer-forming composition containing a radical polymerizable compound (c1) to form a scratch-resistant layer coating film

(IV) a step of forming a scratch-resistant layer by curing the scratch-resistant layer coating film

Process (I) -

The step (I) is a step of applying a resin composition containing a polyorganosilsesquioxane (a1) to a substrate to form a hard coat coating film.

The substrate, the polyorganosilsesquioxane (a1), and the resin composition are as described above.

The method for applying the resin composition is not particularly limited, and a known method can be used. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a bar coating method, a gravure coating method, and a die coating method.

Process (II)

The step (II) is a step of forming a hard coat layer by curing the hard coat layer coating film. The term "curing the hard coat coating film" means that at least a part of the crosslinkable groups of the polyorganosilsesquioxane (a1) contained in the hard coat coating film is polymerized.

The curing of the hard coat coating film is preferably performed by irradiation of ionizing rays or heating.

The type of the ionizing radiation is not particularly limited, and X-rays, electron beams, ultraviolet rays, visible light, infrared rays, and the like can be given, but ultraviolet rays are preferably used. For example,when the hard coat coating film is ultraviolet-curable, it is preferable to irradiate it with an ultraviolet lamp at 10mJ/cm²～2000mJ/cm²The curable compound is cured by the irradiation amount of ultraviolet ray of (1), and when the hard coat film has a scratch-resistant layer on the hard coat layer, the curable compound is preferably semi-cured. More preferably 50mJ/cm 2-1800 mJ/cm²More preferably 100mJ/cm²～1500mJ/cm². As the kind of the ultraviolet lamp, a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used.

When thermally cured, the temperature is not particularly limited, but is preferably 80 ℃ or more and 200 ℃ or less, more preferably 100 ℃ or more and 180 ℃ or less, and further preferably 120 ℃ or more and 160 ℃ or less.

The oxygen concentration during curing is preferably 0 to 1.0 vol%, more preferably 0 to 0.1 vol%, and most preferably 0 to 0.05 vol%.

Process (III)

The step (III) is a step of forming a scratch-resistant layer coating film by applying a scratch-resistant layer forming composition containing a radical polymerizable compound (c1) on the hard coat layer.

The radical polymerizable compound (c1) and the scratch-resistant layer-forming composition are as described above.

The method for applying the scratch-resistant layer-forming composition is not particularly limited, and a known method can be used. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a bar coating method, a gravure coating method, and a die coating method.

Procedure (IV)

The step (IV) is a step of forming a scratch-resistant layer by curing the scratch-resistant layer coating film.

The curing of the scratch-resistant layer coating film is preferably performed by irradiation of ionizing radiation or heating. The irradiation and heating with ionizing radiation are the same as those described in step (II). The curing of the scratch-resistant layer coating film means that at least a part of the radical polymerizable groups of the radical polymerizable compound (c1) contained in the scratch-resistant layer coating film is subjected to a polymerization reaction.

In the present invention, when the hard coat film has a scratch resistant layer on the hard coat layer, the hard coat film is preferably semi-cured in the step (II) described above. That is, it is preferable that the hard coat layer coating film is semi-cured in the step (II), then the scratch resistant layer forming composition is coated on the semi-cured hard coat layer to form the scratch resistant layer coating film in the step (III), and then the scratch resistant layer coating film is cured and the hard coat layer is completely cured in the step (IV). Here, the half-curing of the hard coat coating film means that only a part of the crosslinkable groups of the polyorganosilsesquioxane (a1) contained in the hard coat coating film is polymerized. The semi-curing of the hard coat coating film may be performed by adjusting the irradiation amount of ionizing radiation, or the heating temperature and time.

The drying treatment may be carried out as necessary between the steps (I) and (II), between the steps (II) and (III), between the steps (III) and (IV), or after the step (IV). The drying treatment can be performed by blowing warm air, placing in a heating furnace, transporting in a heating furnace, heating with a roll from a surface (substrate surface) on which the hard coat layer and the scratch-resistant layer are not provided, or the like. The heating temperature is not particularly limited as long as it is a temperature at which the solvent can be dried and removed. Here, the heating temperature refers to the temperature of warm air or the ambient temperature in the heating furnace.

The hard coat film of the present invention is excellent in pencil hardness and repeated bending resistance. Further, the hard coat film of the present invention can be used as a surface protective film for an image display device, for example, a surface protective film for a folding type apparatus (folding type display). The folding device is a device using a flexible display whose display screen is deformable, and can fold a device main body (display) by utilizing the deformability of the display screen.

Examples of the folding device include an organic electroluminescence device.

The present invention also relates to a polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond, wherein,

hydrogen number of 3.0 or more and side chain length of 14X 10^-10～19×10^-10m，

The hydrogen bond value is represented by the following formula (1), and the side chain length represents a length from the Si atom to the end of the side chain.

1, the number of hydrogen atoms capable of forming hydrogen bonds per 1 structural unit, x 1000

Further, the present invention relates to a polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond, wherein,

a hydrogen bond value of 3.0 or more, a crosslinkable group value of 4.5 to 6.0,

the hydrogen bond value is represented by the following formula (1), and the crosslinkable group value is represented by the following formula (5).

1, the number of hydrogen atoms capable of forming hydrogen bonds per 1 structural unit, x 1000

Value of crosslinkable group 1 number of crosslinkable groups/molecular weight of 1 structural unit × 1000

The polyorganosilsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond is the same as the polyorganosilsesquioxane (a1) having a group containing a hydrogen atom capable of forming a hydrogen bond in the resin composition, and the preferable range is the same.

The hydrogen bond value, the side chain length and the crosslinkable group value are the same as those described in the above resin composition, and the preferable ranges are also the same.

In the polyorganosilsesquioxane, the hydrogen number is preferably 3.0 or more, and the side chain length is preferably 14X 10^-10～19×10^-10m, a crosslinkable group value of 4.5 to 6.0.

Examples

The present invention will be described more specifically with reference to examples, but the scope of the present invention should not be construed as being limited thereto.

< preparation of base Material >

(production of polyimide powder)

To a 1L reactor equipped with a stirrer, a nitrogen gas injection device, a dropping funnel, a temperature controller, and a cooler, 832g of N, N-dimethylacetamide (DMAc) was fed under a nitrogen stream, and then the temperature of the reactor was set to 25 ℃. 64.046g (0.2mol) of bistrifluoromethylbenzidine (TFDB) was added thereto and dissolved. While maintaining the resulting solution at 25 ℃, 31.09g (0.07mol) of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 8.83g (0.03mol) of biphenyltetracarboxylic dianhydride (BPDA) were charged and stirred for a certain period of time to react them. 20.302g (0.1mo1) of terephthaloyl chloride (TPC) was added to the solution to obtain a polyamic acid solution having a solid content of 13% by mass. Then, 25.6g of pyridine and 33.1g of acetic anhydride were put into the polyamic acid solution, stirred for 30 minutes, further stirred at 70 ℃ for 1 hour, and then cooled to room temperature. Methanol (20L) was added thereto, and the precipitated solid component was filtered and pulverized. Then, vacuum drying was performed at 100 ℃ for 6 hours, thereby obtaining 111g of polyimide powder.

(preparation of base S-1)

100g of the above polyimide powder was dissolved in 670g of N, N-dimethylacetamide (DMAc) to obtain a 13 mass% solution. The resulting solution was cast onto a stainless steel plate and dried with hot air at 130 ℃ for 30 minutes. Then, the film was peeled off from the stainless steel plate, fixed to a frame by pins, and the frame with the film fixed thereto was put into a vacuum oven, heated for 2 hours while gradually increasing the temperature from 100 ℃ to 300 ℃, and then slowly cooled. The cooled film was separated from the frame, and then, as a final heat treatment step, heat treatment was further performed at 300 ℃ for 30 minutes, thereby obtaining a substrate S-1 made of a polyimide film and having a thickness of 30 μm.

< Synthesis of polyorganosiloxane (SQ1-1) >

300 mmol (53.8g) of 3-aminopropyltrimethoxysilane and 166g of methyl isobutyl ketone were mixed, and the solution was cooled to 5 ℃ or lower. To the cooled solution was added dropwise 300 mmol (42.3g) of 2-acryloyloxyethyl isocyanate, and after the reaction, the temperature was raised to room temperature.

Then, a mixture of 300 mmol (70.3g) of 3- (trimethoxysilyl) propyl acrylate, 7.39g of triethylamine and 434g of acetone was added to the above solution, 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel, and then the mixture was heated to 50 ℃ to conduct a polycondensation reaction for 10 hours.

Then, the reaction solution was cooled, neutralized with 12mL of a 1N (mol/L) aqueous hydrochloric acid solution, and then 600g of 1-methoxy-2-propanol was added thereto, followed by concentration at 50 ℃ under 30mmHg, thereby obtaining a polyorganosilsesquioxane which is a transparent liquid product of a 2-methoxy-1-propanol solution having a solid content of 30 mass% (SQ 1-1).

5mg of the polymer obtained above was dissolved in 0.5mL of heavy chloroform, and measured with BRUKER AVANCE III HD 400MHz (manufactured by Hitachi High-Tech Science Corporation). The results are shown below.

¹H NMR(400MHz，CDCl₃Ppm): delta 6.3-6.5(d, CH of acrylic acid moiety₂＝CHCO₂) Delta 6.0-6.2(m, CH of acrylic acid moiety)₂＝CHCO₂) Delta 5.8-5.9(m, CH of acrylic acid moiety)₂＝CHCO₂) Delta 4.0-4.3(m, CH beside acrylic acid moiety)₂＝CHCO₂CH₂NH of the urea fraction), delta 2.8-3.6(m, CH beside the urea fraction)₂) δ 1.4-1.8(m, CH beside the silyl moiety)₂) δ 0.4-0.8(m, CH of methylene moiety)₂CH₂CH₂Si)

A polyorganosilsesquioxane (SQ1-2) having a modified content molar ratio of each structural unit was synthesized in the same manner as in the synthesis of the polyorganosilsesquioxane (SQ1-1) except that the amount of each monomer used was changed in the synthesis of the polyorganosilsesquioxane (SQ 1-1).

In the synthesis of the polyorganosilsesquioxane (SQ1-1), polyorganosilsesquioxane (SQ2-1) and polyorganosilsesquioxane (SQ2-3) were synthesized in the same manner as in the synthesis of the polyorganosilsesquioxane (SQ1-1), except that the amount of each monomer used was changed from 3- (trimethoxysilyl) propyl acrylate to 3- (trimethoxysilyl) propyl acrylamide.

A polyorganosilsesquioxane (SQ2-2) was synthesized in the same manner as the synthesis of the polyorganosilsesquioxane (SQ2-1) except that the time for the polycondensation reaction was changed to 2 hours in the synthesis of the polyorganosilsesquioxane (SQ 2-1).

(SQ3-1)

300 mmol (34.8g) of 2-hydroxyethyl acrylate, 100g of methyl isobutyl ketone, 300 mmol (61.5g) of isocyanatopropyltrimethoxysilane and 5mg of NEOSTANN U-60050mg were mixed and reacted at 60 ℃ for 5 hours.

Then, a mixture of 300 mmol (70.0g) of acrylamide 3- (trimethoxysilyl) propyl group, 7.39g of triethylamine and 434g of acetone was added to the above solution, 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel, and then the mixture was heated to 50 ℃ to conduct a polycondensation reaction for 10 hours.

Then, the reaction solution was cooled, neutralized with 12mL of 1N aqueous hydrochloric acid solution, then 600g of 1-methoxy-2-propanol was added, and then concentrated under 30mmHg at 50 ℃ to obtain polyorganosilsesquioxane which is a transparent liquid product of a 2-methoxy-1-propanol solution having a solid content of 30 mass% (SQ 3-1).

(SQ4-1)

A polyorganosilsesquioxane (SQ4-1) was synthesized in the same manner as the synthesis of the polyorganosilsesquioxane (SQ3-1) except that the acrylamide 3- (trimethoxysilyl) propyl group was changed to the acrylic acid 3- (trimethoxysilyl) propyl group in the synthesis of the polyorganosilsesquioxane (SQ 3-1).

(SQ5-1)

Acrylamide 2-hydroxyethyl ester (300 mmol, 34.5g), methyl isobutyl ketone (100 g), isopropyltrimethoxysilane (300 mmol, 61.5g), and NEOSTANN U-60050mg were mixed and reacted at 60 ℃ for 5 hours.

Then, a mixture of 300 mmol (70.0g) of acrylamide 3- (trimethoxysilyl) propyl group, 7.39g of triethylamine and 434g of acetone was added to the above solution, 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel, and then the mixture was heated to 50 ℃ to conduct a polycondensation reaction for 10 hours.

Then, the reaction solution was cooled, neutralized with 12mL of 1N aqueous hydrochloric acid solution, then 600g of 1-methoxy-2-propanol was added, and then concentrated under 30mmHg at 50 ℃ to obtain polyorganosilsesquioxane which is a transparent liquid product of a 2-methoxy-1-propanol solution having a solid content of 30 mass% (SQ 5-1).

(SQ6-1)

A mixture of 300 mmol (70.8g) of 3-glycidoxypropyltrimethoxysilane, 300 mmol (70.0g) of acrylamide 3- (trimethoxysilyl) propyl, 7.39g of triethylamine and 434g of acetone was added to the above solution, 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel, and then the mixture was heated to 50 ℃ to conduct polycondensation reaction for 10 hours.

Then, 0.3 mmol (21.6g) of acrylic acid and 50g of p-toluenesulfonic acid were added, and the mixture was reacted at 60 ℃ for 10 hours.

Then, the reaction solution was cooled, neutralized with 12mL of 1N aqueous hydrochloric acid solution, then 600g of 1-methoxy-2-propanol was added, and then concentrated under 30mmHg at 50 ℃ to obtain polyorganosilsesquioxane which is a transparent liquid product of a 2-methoxy-1-propanol solution having a solid content of 30 mass% (SQ 6-1).

(SQ7-1)

300 mmol (53.8g) of 3-aminopropyltrimethoxysilane, 300g of tetrahydrofuran and 300 mmol (30.4g) of triethylamine were mixed, and the solution was cooled to 5 ℃ or lower. 300 mmol (33.6g) of chloroacetic acid chloride was added dropwise to the cooled solution, and after the reaction, the temperature was raised to room temperature.

To the resulting solution were added 300g of ethyl acetate and 300g of water, followed by liquid separation and concentration of the organic phase.

To the resulting concentrate were mixed 300g of tetrahydrofuran, 300 mmol (21.6g) of acrylic acid and 300 mmol (30.4g) of triethylamine, and the mixture was reacted at 50 ℃ for 6 hours. Then, 600g of ethyl acetate and 600g of water were added to the mixture, and the organic phase was concentrated after liquid separation.

To the resulting concentrate was added a mixture of 7.39g of triethylamine and 434g of acetone, and 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel, followed by heating to 50 ℃ for 10 hours of polycondensation. Then, the reaction solution was cooled, neutralized with 12mL of 1N aqueous hydrochloric acid solution, and then 600g of 1-methoxy-2-propanol was added thereto, followed by concentration at 50 ℃ under 30mmHg, thereby obtaining polyorganosilsesquioxane which is a transparent liquid product of a 2-methoxy-1-propanol solution having a solid content of 30 mass% (SQ 7-1).

(SQ8-1)

Acrylamide 3- (trimethoxysilyl) propyl group 300 mmol (70.0g) was added to the concentrate before the polycondensation reaction of (SQ7-1), and then, by the same polycondensation reaction as in (SQ7-1), polyorganosiloxane (SQ8-1) as a transparent liquid product of a 2-methoxy-1-propanol solution having a solid content concentration of 30 mass% was obtained.

(SQ-1x)

600 mmol (69.6g) of 2-hydroxyethyl acrylate, 200g of methyl isobutyl ketone, 600 mmol (123.0g) of isocyanatopropyltrimethoxysilane and 600 mg of NEOSTANN U-60050mg were mixed and reacted at 60 ℃ for 5 hours.

Then, a mixture of 7.39g of triethylamine and 434g of acetone was added to the above solution, 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel, and the mixture was heated to 50 ℃ to conduct a polycondensation reaction for 10 hours.

Then, the reaction solution was cooled, neutralized with 12mL of 1N aqueous hydrochloric acid solution, added with 600g of 1-methoxy-2-propanol, and then concentrated under 30mmHg at 50 ℃ to obtain polyorganosilsesquioxane (SQ-1X), which is a transparent liquid product of a 2-methoxy-1-propanol solution having a solid content of 30 mass%.

(SQ-2x)

600 mmol (107.6g) of 3-aminopropyltrimethoxysilane and 332g of methyl isobutyl ketone were mixed, and the solution was cooled to 5 ℃ or lower. 600 mmol (84.6g) of 2-acryloyloxyethyl isocyanate was added dropwise to the cooled solution, and the temperature was raised to room temperature after the reaction.

Then, a mixture of 7.39g of triethylamine and 434g of acetone was added to the above solution, 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel, and the mixture was heated to 50 ℃ to conduct a polycondensation reaction for 10 hours.

Then, the reaction solution was cooled, neutralized with 12mL of 1N aqueous hydrochloric acid solution, added with 600g of 1-methoxy-2-propanol, and then concentrated under 30mmHg at 50 ℃ to obtain polyorganosilsesquioxane (SQ-2X), which is a transparent liquid product of a 2-methoxy-1-propanol solution having a solid content of 30 mass%.

(SQ-3x)

A mixture of 600 mmol (140.0g) of 3- (trimethoxysilyl) propyl acrylamide, 7.39g of triethylamine and 434g of acetone was added to the above solution, 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel, and the mixture was heated to 50 ℃ to conduct polycondensation reaction for 10 hours.

Then, the reaction solution was cooled, neutralized with 12mL of 1N aqueous hydrochloric acid solution, and then 600g of 1-methoxy-2-propanol was added, followed by concentration at 50 ℃ under 30mmHg, thereby obtaining a polyorganosilsesquioxane (SQ-3X) which is a transparent liquid product of a 2-methoxy-1-propanol solution having a solid content of 30 mass%.

(SQ-4x)

A2 mol/L methylamine solution in methanol (120 mmol, 60mL) and 166g of methyl isobutyl ketone were mixed, and the solution was cooled to 5 ℃ or lower. To the cooled solution was added dropwise 120 mmol (16.9g) of 2-acryloyloxyethyl isocyanate, and the temperature was raised to room temperature after the reaction.

Then, a mixture of 480 mmol (112.5g) of 3- (trimethoxysilyl) propyl acrylate, 7.39g of triethylamine and 434g of acetone was added to the above solution, 73.9g of pure water was added dropwise over 30 minutes using a dropping funnel, and the mixture was heated to 50 ℃ to conduct a polycondensation reaction for 10 hours.

Then, the reaction solution was cooled, neutralized with 12mL of 1N aqueous hydrochloric acid solution, and then 600g of 1-methoxy-2-propanol was added, followed by concentration at 50 ℃ under 30mmHg, thereby obtaining a polyorganosilsesquioxane (SQ-4X) which is a transparent liquid product of a 2-methoxy-1-propanol solution having a solid content of 30 mass%.

(SQ-5x)

A mixture of 600 mmol (141.6g) of 3-glycidoxypropyltrimethoxysilane, 7.39g of triethylamine and 434g of acetone was added to the above solution, 73.9g of pure water was added dropwise over 30 minutes from the dropping funnel, and the mixture was heated to 50 ℃ to conduct polycondensation reaction for 10 hours.

Then, the reaction solution was cooled, neutralized with 12mL of 1N aqueous hydrochloric acid solution, and then 600g of 1-methoxy-2-propanol was added, followed by concentration at 50 ℃ under 30mmHg, thereby obtaining a polyorganosilsesquioxane (SQ-5X), which is a transparent liquid product of a 2-methoxy-1-propanol solution having a solid content of 30 mass%.

The structures of the respective polymers used as the polyorganosilsesquioxane (a1) are shown below. In the following structural formula, "SiO 15" represents a silsesquioxane unit. The structural units of the respective polymers correspond to the structural unit (a) and the structural unit (B) in this order from the structural unit shown on the left side, and the composition ratio of the respective structural units is represented by a molar ratio.

Table 1 shows the hydrogen key value, the side chain length, the number of side chain elements, and the value of crosslinkable groups of each polymer calculated by the above-described method.

[ chemical formula 16]

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

[ chemical formula 21]

[ example 1]

< preparation of resin composition >

(resin composition HC-1)

Irgacure 127(Irg.127) (radical polymerization initiator) and MIBK (methyl isobutyl ketone) were added to a 2-methoxy-1-propanol solution containing the above-mentioned polyorganosilsesquioxane (SQ1-1), and the contents of the respective components were adjusted as follows, and then the mixture was put into a mixing tank and stirred. The obtained composition was filtered through a polypropylene filter having a pore size of 0.45 μm to obtain resin composition HC-1.

90.4 parts by mass of a 2-methoxy-1-propanol solution (solid content concentration: 30% by mass) of polyorganosilsesquioxane (SQ1-1)

Irgacure 127(Irg.127) 5.0 parts by mass

4.6 parts of MIBK by mass

Irgacure 127(irg.127) is a radical polymerization initiator manufactured by BASF.

(production of hard coating film)

A polyimide substrate S-1 having a thickness of 30 μm was coated with the resin composition HC-1 by a wire bar #18 to a film thickness of 18 μm after curing, and a hard coat coating film was formed on the substrate.

Subsequently, the hard coat film was dried at 120 ℃ for 1 minute, and then irradiated with 18mW/cm of illumination using an air-cooled mercury lamp at 25 ℃ and an oxygen concentration of 100ppm (parts per million)²The dose of irradiation was 160mJ/cm²Ultraviolet rays of (1). The hard coat coating film was cured in this way, and a laminate (hard coat film) of example 1 having a hard coat layer on the substrate was obtained.

Examples 2 to 11 and comparative examples 1 to 5

Hard coating films of examples 2 to 11 and comparative examples 1 to 5 were produced in the same manner as in example 1 except that the polyorganosilsesquioxane (SQ1-1) used was changed to (SQ1-2) to (SQ8-1) and (SQ-1x) to (SQ-5 x).

[ evaluation of hard coating film ]

The hard coat films of the respective examples and comparative examples produced were evaluated in the following manner. The evaluation results are shown in table 1.

(Pencil hardness)

The pencil hardness was evaluated in accordance with JIS (Japanese Industrial Standards, JIS) K5400. After the hard coat films of the examples and comparative examples were wetted at 25 ℃ and 60% relative humidity for 2 hours, 5 different positions on the surface of the hard coat layer were scratched with a load of 4.9N using a test pencil of H to 9H specified in JIS S6006. Then, of the pencil hardnesses at 0 to 2 points where the scratch was visually observed, the pencil hardness with the highest hardness was used as the evaluation result. The higher the value described before "H", the higher the hardness, and the more preferable the pencil hardness.

(repeated bending resistance)

Sample films having a width of 15mm and a length of 150mm were cut out from the hard coat films of the respective examples and comparative examples, and the films were left to stand at a temperature of 25 ℃ and a relative humidity of 65% for 1 hour or more. Thereafter, a repeated bending resistance test was performed using a 180 ° folding resistance tester (model IMC-0755 manufactured by Imoto mechanical co., LTD) with the substrate inside. In the test machine used, the test was repeated 1 time by the operation of bending the sample film at a bending angle of 180 ° at the center portion in the longitudinal direction along the curved surface of a rod (cylinder) having a diameter of 4mm and then recovering (spreading the sample film).

The evaluation of no cracking was made when the 180 ° bend test was repeated 30 ten thousand or more times was a, the evaluation of cracking was made 10 ten thousand or more and less than 30 ten thousand times was B, and the evaluation of cracking was made less than 10 ten thousand times was C.

In addition, whether cracks were generated was visually evaluated.

As shown in Table 1, the hard coat films of examples 1 to 11 were excellent in pencil hardness and repeated bending resistance.

Industrial applicability

The present invention can provide a resin composition for providing a hard coat film having excellent pencil hardness and excellent repeated bending resistance, a hard coat film having a hard coat layer containing a cured product of the resin composition, and a polyorganosilsesquioxane.

While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

The present application claims priority based on the japanese patent application (japanese patent application 2019-93792) filed on 5/17/2019, the contents of which are incorporated by reference in the present specification.