WO2020235383A1

WO2020235383A1 - Resin composition, hard coating film and polyorganosilsesquioxane

Info

Publication number: WO2020235383A1
Application number: PCT/JP2020/018872
Authority: WO
Inventors: 裕三永田; 暢之芥川; 北村　哲; 顕夫田村
Original assignee: 富士フイルム株式会社
Priority date: 2019-05-17
Filing date: 2020-05-11
Publication date: 2020-11-26
Also published as: JPWO2020235383A1; JP7142158B2; CN113840854B; CN113840854A; KR20210144791A

Abstract

The present invention provides: a resin composition which contains a polyorganosilsesquioxane that has a group containing a hydrogen atom that is capable of forming a hydrogen bond, wherein the polyorganosilsesquioxane has a hydrogen bond value of 3.0 or more and a side chain length of from 14 × 10^-10 m to 19 × 10^-10 m; the resin composition wherein the polyorganosilsesquioxane has a hydrogen bond value of 3.0 or more and a crosslinkable group value of from 4.5 to 6.0; a hard coating film which comprises a hard coating layer that is obtained by curing the above-described resin composition; and a polyorganosilsesquioxane.

Description

Resin composition, hard coat film, and polyorganosylsesquioxane

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

Display devices using cathode ray tubes (CRT), plasma display (PDP), electroluminescence display (ELD), vacuum fluorescent display (VFD), field emission display (FED), and image display devices such as liquid crystal display (LCD). Therefore, in order to prevent the display surface from being scratched, it is preferable to provide a hard coat film having a hard coat layer on the base material.

As a resin composition for forming a hard coat layer, a resin composition containing polyorganosis sesquioxane is known.
For example, Patent Document 1 describes an active energy ray-curable composition containing a silsesquioxane compound in which at least one of the organic groups directly bonded to a silicon atom is an organic group having a urea bond and one (meth) acryloyloxy group. Is described. Further, Patent Document 2 describes an organosilane having a UV curable group, a thermosetting silane group, and a cross-linking group having at least two carbon atoms that bond the UV curable group and the thermosetting silane group. Liquid coating agent mixtures containing hydrolyzed and condensed compounds are described.

International Publication No. 2010/067685 Japan Special Table 2011-518666

In recent years, for example, in smartphones and the like, there has been an increasing need for an ultra-thin and flexible display, and along with this, an optical film capable of achieving both hardness and repeated bending resistance (property that cracks do not occur even when repeatedly bent). Is strongly sought after.
As a result of studies by the present inventors, it was found that the hard coat film using the resin composition described in Patent Documents 1 and 2 cannot have both pencil hardness and repeated bending resistance.
An object of the present invention is a resin composition that gives a hard coat film having excellent pencil hardness and repeated bending resistance, a hard coat film having a hard coat layer containing a cured product of the above resin composition, and polyorganosylsesquioxane. To provide.

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

<1>
A resin composition containing a polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The hydrogen bond value of the polyorganosylsesquioxane is 3.0 or more, and the side chain length is 14 × ^10-10 to 19 × ^10-10 m.
The hydrogen bond value is represented by the following formula (1), and the side chain length represents the length from the Si atom to the end of the side chain, a resin composition.

Hydrogen bond value = number of hydrogen atoms that can form hydrogen bonds in one structural unit / molecular weight of one structural unit x 1000 ... (1)

<2>
A resin composition containing a polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The polyorganosylsesquioxane has a hydrogen bond value of 3.0 or more and a crosslinkable base value of 4.5 to 6.0.
The hydrogen bond value is represented by the following formula (1), and the crosslinkable base value is represented by the following formula (5).

Crosslinkable radix = number of crosslinkable groups in 1 structural unit / molecular weight of 1 structural unit x 1000 ... (5)

<3>
The polyorganosylsesquioxane has a hydrogen bond value of 3.0 or more, a side chain length of 14 × ^10-10 to 19 × ^10-10 m, and a crosslinkable base value of 4.5 to 6.0. The resin composition according to <1> or <2>.
<4>
The item 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. Resin composition.
<5>
A structural unit (S1) in which the polyorganosylsesquioxane has a group containing a hydrogen atom capable of forming a hydrogen bond, and a structural unit (S2) having a crosslinkable group different from the structural unit (S1). The resin composition according to any one of <1> to <4>, which contains and.

<6>
The resin composition according to <5>, wherein the group containing a hydrogen atom capable of forming a hydrogen bond of 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 contained in the structural unit (S2) is a (meth) acrylamide group.

<9>
The resin composition according to any one of claims 1 to 8, wherein the polyorganosylsesquioxane has a weight average molecular weight of 10,000 to 1,000,000.
<10>
A hard coat film having a base material and a hard coat layer containing a cured product of the resin composition according to any one of <1> to <9>.
<11>
The hard coat film according to <10>, which has a pencil hardness of 3H or more and does not generate cracks when a 180 ° bending test is repeated 100,000 times with a radius of curvature of 2 mm with the base material inside.

<12>
A polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The hydrogen bond value is 3.0 or more, the side chain length is 14 × 10 ^-10 to 19 × 10 ^-10 m, and the side chain length is 14 × 10 ^-10 to 19 × 10 ^-10 m.
The hydrogen bond value is represented by the following formula (1), and the side chain length is a polyorganosylsesquioxane in which the side chain length represents the length from the Si atom to the end of the side chain.

<13>
A polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The hydrogen bond value is 3.0 or more, the crosslinkable base value is 4.5 to 6.0, and
The hydrogen bond value is represented by the following formula (1), and the crosslinkable base value is a polyorganosylsesquioxane represented by the following formula (5).

<14>
<12> or <13> having a hydrogen bond value of 3.0 or more, a side chain length of 14 × ^10-10 to 19 × ^10-10 m, and a crosslinkable base value of 4.5 to 6.0. Polyorganosylsesquioxane as described in.

According to the present invention, a resin composition that gives a hard coat film having excellent pencil hardness and repeated bending resistance, a hard coat film having a hard coat layer containing a cured product of the above resin composition, and polyorganosylsesquioxane. Can be provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail, but the present invention is not limited thereto. In this specification, when the numerical values represent physical property values, characteristic values, etc., the description of "(numerical value 1) to (numerical value 2)" means "(numerical value 1) or more (numerical value 2) or less". .. Further, in the present specification, the description of "(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 is a resin composition containing a polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The polyorganosilsesquioxane hydrogen valency Sun is 3.0 or more, a side chain length ^{^{14 × 10 -10 ~ 19 × 10}} -10 m (14 ~ 19Å),
The hydrogen bond value is represented by the following formula (1), and the side chain length represents the length from the Si atom to the end of the side chain, and relates to a resin composition.
Hydrogen bond value = number of hydrogen atoms that can form hydrogen bonds in one structural unit / molecular weight of one structural unit x 1000 ... (1)

Further, the present invention is a resin composition containing a polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The polyorganosylsesquioxane has a hydrogen bond value of 3.0 or more and a crosslinkable base value of 4.5 to 6.0.
The hydrogen bond value is represented by the following formula (1), and the crosslinkable base value is also related to the resin composition represented by the following formula (5).
Hydrogen bond value = number of hydrogen atoms that can form hydrogen bonds in one structural unit / molecular weight of one structural unit x 1000 ... (1)
Crosslinkable radix = number of crosslinkable groups in one structural unit / molecular weight of one structural unit x 1000 ... (5)

<Polyorganosylsesquioxane (a1) having a group containing a hydrogen atom capable of forming a hydrogen bond>
A polyorganosylsesquioxane (a1) having a group containing a hydrogen atom capable of forming a hydrogen bond (also referred to as “polyorganosylsesquioxane (a1)”) will be described.

(Group containing hydrogen atom that can form hydrogen bond)
Polyorganosylsesquioxane (a1) has a group containing a hydrogen atom capable of forming a hydrogen bond. A hydrogen atom capable of forming a hydrogen bond is a hydrogen atom covalently bonded to an atom having a high electronegativity, and can form a hydrogen bond with nitrogen, oxygen, etc. located in the vicinity.
As the group containing a hydrogen atom capable of forming a hydrogen bond possessed by the polyorganosylsesquioxane (a1), a generally known group containing a hydrogen atom capable of forming a hydrogen bond can be used, and an amide group, It is preferably at least one group selected from a urethane group, a urea group, and a hydroxyl group, and more preferably at least one group selected from an amide group, a urethane group, and a urea group.
In the present invention, the amide group represents a divalent linking group represented by -NH-C (= O)-, and the urethane group is represented by -NH-C (= O) -O-. It represents a divalent linking group, and the urea group represents a divalent linking group represented by -NH-C (= O) -NH-.

(Hydrogen bond value)
In the present invention, the hydrogen bond value represents the density of hydrogen atoms capable of forming a hydrogen bond in the polyorganosylsesquioxane (a1), and is calculated from the following formula (1).

When the hydrogen atom capable of forming a hydrogen bond is an amide group, the number of hydrogen atoms contained in the amide group capable of forming a hydrogen bond is 1, 1 for a urethane group, 2 for a urea group, and a hydroxyl group. In the case of, it is counted as 1.
The structural unit is a repeating unit possessed by the polyorganosylsesquioxane (a1). For example, when the polyorganosylsesquioxane (a1) is a polymer obtained by polymerizing only one kind of monomer. The polyorganosylsesquioxane (a1) has one structural unit, and in the case of a copolymer of two types of monomers, the constituent unit is two.

When the polyorganosylsesquioxane (a1) has one structural unit, the hydrogen bond value of the polyorganosylsesquioxane (a1) is the hydrogen bond value in one structural unit calculated by the above formula (1). It becomes.

When the polyorganosylsesquioxane (a1) has a plurality of structural units, the hydrogen bond fraction in each structural unit calculated by the above formula (1) is added to each structural unit in the polyorganosylsesquioxane (a1). The sum of the values obtained by multiplying the composition ratio (mol%) of the above and dividing by 100 (average value of mole fraction) is taken as the hydrogen bond value of polyorganosylsesquioxane (a1).

Specifically, when the polyorganosylsesquioxane (a1) has two types of structural units (constituent unit 1 and structural unit 2), the hydrogen bond value of the polyorganosylsesquioxane (a1) is as follows. It is calculated from the following formula (2A).

Hydrogen bond value = H ₁ (hydrogen bond value of structural unit 1) x W ₁ (composition ratio of structural unit 1 (mol%)) / 100 + H ₂ (hydrogen bond value of structural unit 2) x W ₂ (hydrogen bond value of structural unit 2) Composition ratio (mol%)) / 100 ... (2A)

In addition, polyorganosylsesquioxane (a1) is a constituent unit 1, a constituent unit 2, ... .. When having the structural unit X (X represents an integer of 3 or more), the hydrogen bond value of the polyorganosylsesquioxane (a1) is calculated from the following formula (2B).

Hydrogen bond value = H ₁ (hydrogen bond value of structural unit 1) x W ₁ (composition ratio of structural unit 1 (mol%)) / 100 + H ₂ (hydrogen bond value of structural unit 2) x W ₂ (hydrogen bond value of structural unit 2) Composition ratio (mol%)) / 100+ ... H _X (hydrogen bond value of constituent unit X) x W _X (composition ratio of constituent unit X (mol%)) / 100 ... (2B)

In the present invention, the polyorganosylsesquioxane (a1) has a hydrogen atom capable of forming a hydrogen bond so that the hydrogen bond value is 3.0 or more. As a result, it is possible to increase the density of hydrogen bonds formed by the polyorganosylsesquioxane (a1), and it is presumed that the pencil hardness of the hard coat film can be increased. In addition, hydrogen bonds can be reversibly split and recombined, and even if the hydrogen bonds are split when the hard coat film is bent and deformed, they can be rebonded after the deformation is resolved. It is presumed that a hard coat film that is resistant to bending deformation can be obtained without lowering it.

The hydrogen bond 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 from the viewpoint of the productivity of polyorganosylsesquioxane, more preferably 15 or less, and 10 or less. Is even more preferable.

(Side chain length)
In one aspect of the invention, the polyorganosylsesquioxane (a1) has a side chain having a side chain length of 14 × ^10-10 to 19 × ^10-10 m.
The side chain is a chain bonded to a Si atom in polyorganosylsesquioxane (a1) and means a chain other than the structural portion composed of a siloxane bond (Si—O—Si).

The side chain length represents the length from the Si atom to the end of the side chain, and is determined by using "Winmostar" manufactured by X-Ability. In calculating the value of the side chain length, first, the chemical structure from the Si atom to the end of the side chain is input, then the most stable conformation is obtained by MOPAC (AM1), and then "molecular weight area, volume". From the item "Vander Walls"
Execute "Molecular Surface" and obtain the numerical value of "Maximum Length Molecule".

When polyorganosilsesquioxane (a1) has one type of side chain, that is, has one type of structural unit, the side chain length calculated in one structural unit is the side of polyorganosilsesquioxane (a1). The chain length.

When the polyorganosylsesquioxane (a1) has a plurality of types of side chains, that is, has a plurality of types of structural units, the side chain length calculated for each structural unit is used in the polyorganosylsesquioxane (a1). The sum of the values obtained by multiplying the composition ratio (mol%) of each constituent unit and dividing by 100 (mean value of mole fraction) is taken as the side chain length of polyorganosylsesquioxane (a1).

Specifically, when the polyorganosylsesquioxane (a1) has two types of structural units (constituent unit 1 and structural unit 2), the side chain length of the polyorganosylsesquioxane (a1) is as follows. It is calculated from the following formula (3A).

Side chain length = L ₁ (side chain length of structural unit 1) x W ₁ (composition ratio of structural unit 1 (mol%)) / 100 + L ₂ (side chain length of structural unit 2) x W ₂ (side chain length of structural unit 2) Composition ratio (mol%)) / 100 ... (3A)

In addition, polyorganosylsesquioxane (a1) is a constituent unit 1, a constituent unit 2, ... .. When the structural unit X (X represents an integer of 3 or more) is provided, the side chain length of the polyorganosylsesquioxane (a1) is calculated from the following formula (3B).

Side chain length = L ₁ (side chain length of structural unit 1) x W ₁ (composition ratio of structural unit 1 (mol%)) / 100 + L ₂ (side chain length of structural unit 2) x W ₂ (composition unit 2) composition ratio _{(mol%)) / 100+ ... L X} ( side chain length of structural units X) × _{W X} (the composition of the structural unit X ratio (molar%)) / 100 ··· (3B )

The longer the side chain, the more flexible the structure of the polyorganosylsesquioxane (a1) is, and the better the resistance to repeated bending of the hard coat film. On the other hand, the shorter the side chain, the harder the structure of polyorganosylsesquioxane (a1), and the better the pencil hardness of the hard coat film.
In the present invention, by setting the side chain length of the polyorganosylsesquioxane (a1) to 14 × 10 ^-10 to 19 × 10 ^-10 m, it is possible to achieve both resistance to repeated bending and pencil hardness.
The side chain length is preferably 15 × 10 ^-10 to 18 × 10 ^-10 m, more preferably 16 × 10 ^-10 to 17 × 10 ^-10 m.

The number of elements contained in the side chain is preferably 8 to 11, more preferably 9 or 10.
The number of elements possessed by the side chain represents the number of elements constituting the main chain in the side chain, and the elements branched from the main chain are excluded. For example, the number of elements in the i-propyl group is 2, and the number of elements in the 3-acryloyloxypropyl group is 7.
When polyorganosilsesquioxane (a1) has one type of side chain, that is, has one type of structural unit, the number of elements in the side chain in one structural unit is the number of elements of polyorganosilsesquioxane (a1). The number of elements in the side chain.

Further, when the polyorganosylsesquioxane (a1) has a plurality of types of side chains, that is, has a plurality of types of structural units, the number of elements contained in the side chains in each structural unit is added to the polyorganosylsesquioxane (a1). The sum of the values obtained by multiplying the composition ratio (mol%) of each structural unit in a1) and dividing by 100 (mean mole fraction) is taken as the number of elements in the side chain of polyorganosylsesquioxane (a1).

Specifically, when the polyorganosylsesquioxane (a1) has two types of structural units (constituent unit 1 and structural unit 2), the number of elements in the side chain of the polyorganosylsesquioxane (a1) is , Calculated from the following formula (4A).

Number of elements in the side chain of polyorganosylsesquioxane (a1) = N ₁ (number of elements in structural unit 1) x W ₁ (composition ratio of structural unit 1 (mol%)) / 100 + N ₂ (composition unit 2) Number of elements) x W ₂ (composition ratio of constituent unit 2 (mol%)) / 100 ... (4A)

In addition, polyorganosylsesquioxane (a1) is a constituent unit 1, a constituent unit 2, ... .. When the structural unit X (X represents an integer of 3 or more) is provided, the number of elements contained in the side chain of the polyorganosylsesquioxane (a1) is calculated from the following formula (4B).

Number of elements in the side chain of polyorganosylsesquioxane (a1) = N ₁ (number of elements in structural unit 1) x W ₁ (composition ratio of structural unit 1 (mol%)) / 100 + N ₂ (composition unit 2) (composition ratio of the structural unit 2 (mol%) number of elements) × _{W 2)} / 100+ ... N _X (number of elements of the structural unit X) × _{W X} (the composition of the structural unit X ratio (mol%)) / 100 ...・ (4B)

(Crosslinkable base value)
In one aspect of the invention, the polyorganosylsesquioxane (a1) has a crosslinkable group.
The crosslinkable group is not particularly limited as long as it can form a covalent bond by reacting, and examples thereof include a radical polymerizable crosslinkable group and a cationically polymerizable crosslinkable group.

As the radically polymerizable crosslinkable group, a generally known radically polymerizable crosslinkable group can be used. Examples of the radically polymerizable crosslinkable group include a polymerizable unsaturated group, and specific examples thereof include a vinyl group, an allyl group, a (meth) acryloyloxy group, a (meth) acrylamide group, and the like, and (meth) acryloyl. An oxy group or a (meth) acrylamide group is preferable. In addition, each group mentioned above may have a substituent.

The above-mentioned (meth) acrylamide group exemplified as a crosslinkable group has an amide group inherent in it, and also corresponds to a group containing a hydrogen atom capable of forming a hydrogen bond.

As the cationically polymerizable crosslinkable group, a generally known cationically polymerizable crosslinkable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, and a spirororso. Examples thereof include an ester group and a vinyloxy group. As the cationically polymerizable group, an alicyclic ether group and a vinyloxy group are preferable, and an epoxy group and an oxetanyl group are particularly preferable. The epoxy group may be an alicyclic epoxy group (a group having a condensed ring structure of an epoxy group and an alicyclic group). In addition, each group mentioned above may have a substituent.

The crosslinkable group of polyorganosylsesquioxane (a1) is preferably a radically polymerizable crosslinkable group, and is at least one group selected from a (meth) acryloyloxy group and a (meth) acrylamide group. Is more preferable.

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

When polyorganosylsesquioxane (a1) has one kind of constituent unit, the crosslinkable base value calculated in one constituent unit is used as the crosslinkable base value of polyorganosylsesquioxane (a1).

When the polyorganosilsesquioxane (a1) has a plurality of types of structural units, the crosslinkable base value in each structural unit calculated by the above formula (5) is added to the polyorganosilsesquioxane (a1). The sum of the values obtained by multiplying the composition ratio (mol%) of each constituent unit and dividing by 100 (mean value of mole fraction) is taken as the crosslinkable base value of polyorganosylsesquioxane (a1).

Specifically, when the polyorganosylsesquioxane (a1) has two structural units (constituent unit 1 and structural unit 2), the crosslinkable base value of the polyorganosylsesquioxane (a1) is as follows. It is calculated from the following formula (6A).

Crosslinkable base value = C ₁ (crosslinkable base value of structural unit 1) x W ₁ (composition ratio of structural unit 1 (mol%)) / 100 + C ₂ (crosslinkable base value of structural unit 2) x W ₂ (composition) Composition ratio of unit 2 (mol%)) / 100 ... (6A)

In addition, polyorganosylsesquioxane (a1) is a constituent unit 1, a constituent unit 2, ... .. When having a structural unit X (X represents an integer of 3 or more), the crosslinkable base value of polyorganosylsesquioxane (a1) is calculated from the following formula (6B).

Crosslinkable base value = C ₁ (crosslinkable base value of structural unit 1) x W ₁ (composition ratio of structural unit 1 (mol%)) / 100 + C ₂ (crosslinkable base value of structural unit 2) x W ₂ (composition) Unit 2 composition ratio (mol%)) / 100+ ... Cx (side chain length of structural unit X) x WW _X (composition ratio of structural unit X (mol%)) / 100 ... (6B)

The smaller the crosslinkability base value, the more flexible the structure of the polyorganosylsesquioxane (a1) is, and the better the resistance to repeated bending of the hard coat film. On the other hand, the larger the crosslinkable base value, the harder the structure of polyorganosylsesquioxane (a1), and the better the pencil hardness of the hard coat film can be.
In the present invention, by setting the crosslinkable base value of polyorganosylsesquioxane (a1) to 4.5 to 6.0, it is possible to achieve both resistance to repeated bending and pencil hardness.
The crosslinkable base value is preferably 4.8 to 5.8, and more preferably 5.0 to 5.5.

Polyorganosylsesquioxane (a1) has a hydrogen bond value of 3.0 or more, a side chain length of 14 × ^10-10 to 19 × ^10-10 m, and a crosslinkable base value of 4. It is more preferably 5 to 6.0.

The polyorganosylsesquioxane (a1) may be a polymer obtained by polymerizing only one kind of monomer, or may be a copolymer of two or more kinds of monomers. From the viewpoint of the productivity of polyorganosylsesquioxane having a desired hydrogen bond value, side chain length, and crosslinkable base value, a copolymer of two or more kinds of monomers is preferable, and a hydrogen bond is formed. More preferably, it is a copolymer of a monomer having a group containing a possible hydrogen atom and a monomer having a crosslinkable group.

The polyorganosylsesquioxane (a1) has a structural unit (S1) having a group containing a hydrogen atom capable of forming a hydrogen bond and a structural unit (S2) having a crosslinkable group different from the structural unit (S1). ) And is preferably contained.

-A structural unit 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 of the structural unit (S1) is preferably at least one selected from an amide group, a urethane group, a urea group, and a hydroxyl group, preferably an amide group, a urethane group, and the like. And at least one selected from the urea group is more preferable.
At least one hydrogen atom capable of forming a hydrogen bond may be contained in the structural unit (S1), and it is preferable that one or two hydrogen atoms are contained.

The structural unit (S1) preferably further has a crosslinkable group. As the crosslinkable group, a radically polymerizable crosslinkable group is preferable, a vinyl group, an allyl group, a (meth) acryloyloxy group, or a (meth) acrylamide group is more preferable, and a (meth) acryloyloxy group or ( A meta) acrylamide group is more preferable, and an acryloyloxy group or an acrylamide group is particularly preferable.

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

In the general formula (S1-1),
L ₁₁ represents a substituted or unsubstituted alkylene group.
R ₁₁ represents a single bond, -NH-, -O-, -C (= O)-, or a divalent linking group obtained by combining these.
L ₁₂ represents a substituted or unsubstituted alkylene group.
Q ₁₁ represents a crosslinkable group.
However, 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 _1.5 ” in the general formula (S1-1) represents a structural portion composed of a siloxane bond (Si—O—Si) in the polyorganosylsesquioxane.
Polyorganosilsesquioxane is a network-type polymer or polyhedral cluster having a siloxane structural unit (silsesquioxane unit) derived from a hydrolyzable trifunctional silane compound, and has a random structure, a ladder structure, or a ladder structure due to siloxane bonds. It can form a cage structure or the like. In the present invention, the structural portion represented by "SiO _1.5 " may have any of the above structures, but preferably contains a large amount of rudder structure. By forming the rudder structure, the deformation recovery of the hard coat film can be kept good. The formation of the rudder structure is qualitatively determined by the presence or absence of absorption derived from Si-O-Si expansion and contraction, which is characteristic of the rudder structure appearing near 1020-1050 cm ^-1 when FT-IR (Fourier Transform Infrared Spectroscopy) is measured. You can check.

In the general formula (S1-1), L ₁₁ represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, for example, a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, an i-propylene group, n. Examples thereof include a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group and an n-decylene group.
Examples of the substituent when the alkylene group represented by L ₁₁ 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 and a silyl group.
L ₁₁ is preferably an unsubstituted linear alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or an n-propylene group, and even more preferably an n-propylene group.

In the general formula (S1-1), R ₁₁ represents a single bond, -NH-, -O-, -C (= O)-, or a divalent linking group obtained by combining these.
As a divalent linking group obtained by combining -NH-, -O-, and -C (= O)-, * -NH-C (= O)-**, * -C (= O) -NH -**, * -NH-C (= O) -O-**, * -OC (= O) -NH-**, -NH-C (= O) -NH-, * -C ( = O) -O-**, * -OC (= O) -**, and the like. * Represents the bond with L ₁₁ in the general formula (S1-1), and ** represents the bond with L ₁₂ in the general formula (S1-1).

R ₁₁ is -NH-C (= O) -NH-, * -NH-C (= O) -O-**, * -NH-C (= O) -**, or -O-. It is preferably -NH-C (= O) -NH-, * -NH-C (= O) -O-**, or * -NH-C (= O)-**. ..

In the general formula (S1-1), L ₁₂ represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, for example, a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, an i-propylene group, n. Examples thereof include a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group and an n-decylene group.
Examples of the substituent when the alkylene group represented by L ₁₂ 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 and a silyl group.
L ₁₂ 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 further preferably a methylene group or an ethylene group. preferable.

In the general formula _{(S1-1), Q 11} represents a crosslinkable group. As the crosslinkable group, a radically polymerizable crosslinkable group is preferable, a vinyl group, an allyl group, a (meth) acryloyloxy group, or a (meth) acrylamide group is more preferable, and a (meth) acryloyloxy group or ( A meta) acrylamide group is more preferable, and an acryloyloxy group or an acrylamide group is particularly preferable.

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 one or two hydrogen atoms capable of forming a hydrogen bond are contained in the structural unit represented by the general formula (S1-1).
The hydrogen atom capable of forming a hydrogen bond is preferably contained as an amide group, a urethane group, or a urea group in R ₁₁ in the general formula (S1-1).

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

In the general formula (S1-2),
L ₁₁ represents a substituted or unsubstituted alkylene group.
r ₁₁ represents a single bond, -NH-, or -O-
L ₁₂ represents a substituted or unsubstituted alkylene group.
q ₁₁ represents -NH- or -O-
q ₁₂ represents a hydrogen atom or a methyl group.

“SiO _1.5 ” in the general formula (S1-2) represents a structural portion composed of a siloxane bond (Si—O—Si) in the polyorganosylsesquioxane.

In the general formula (S1-2), L ₁₁ represents a substituted or unsubstituted alkylene group. L ₁₁ has the general formula (S1-1) in the same meaning as _{L 11} of, and preferred examples are also the same.
In the general formula (S1-2), L ₁₂ represents a substituted or unsubstituted alkylene group. L ₁₂ has the same meaning as the general formula (S1-1) _{L 12} of, and preferred examples are also the same.
q ₁₂ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

-Constituent unit having a crosslinkable group (S2)-
The structural unit (S2) has a crosslinkable group. As the crosslinkable group, a radically polymerizable crosslinkable group is preferable, a vinyl group, an allyl group, a (meth) acryloyloxy group, or a (meth) acrylamide group is more preferable, and a (meth) acryloyloxy group or ( It is more preferably 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).

In the general formula (S1-2),
L ₂₁ represents a substituted or unsubstituted alkylene group.
Q ₂₁ represents a crosslinkable group.

“SiO _1.5 ” in the general formula (S2-1) represents a structural portion composed of a siloxane bond (Si—O—Si) in the polyorganosylsesquioxane.

In the general formula (S2-1), L ₂₁ represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, for example, a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, an i-propylene group, n. Examples thereof include a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group and an n-decylene group.
Examples of the substituent when the alkylene group represented by L ₁₁ 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 and a silyl group.
L ₁₁ is preferably an unsubstituted linear alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or an n-propylene group, and even more preferably an n-propylene group.

In the general formula (S2-1), Q ₂₁ represents a crosslinkable group. As the crosslinkable group, a radically polymerizable crosslinkable group is preferable, a vinyl group, an allyl group, a (meth) acryloyloxy group, or a (meth) acrylamide group is more preferable, and a (meth) acryloyloxy group or ( It is more preferably a meta) acrylamide group.

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

In the general formula (S2-2),
L ₂₁ represents a substituted or unsubstituted alkylene group.
q ₂₁ represents -NH- or -O-
q ₂₂ represents a hydrogen atom or a methyl group.

“SiO _1.5 ” in the general formula (S2-2) represents a structural portion composed of a siloxane bond (Si—O—Si) in the polyorganosylsesquioxane.

In the general formula (S2-2), L ₂₁ represents a substituted or unsubstituted alkylene group. L ₂₁ has the general formula (S2-1) in the same meaning as _{L 21} of, and preferred examples are also the same.
q ₂₁ represents -NH- or -O-, and is preferably -NH-.
q ₂₂ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

The polyorganosylsesquioxane (a1) preferably contains a structural unit represented by the general formula (S1-1) and a structural unit represented by the general formula (S2-1). It is more preferable to contain the structural unit represented by the general formula (S1-2) and the structural unit represented by the general formula (S2-2).

When the polyorganosylsesquioxane (a1) has the constituent units (S1) and (S2), the molar ratio of the constituent units (S1) is more than 1 mol% and 90 mol% or less with respect to all the constituent units. It is more preferably 15 mol% or more and 75 mol% or less, and further preferably 35 mol% or more and 65 mol% or less.

When the polyorganosylsesquioxane (a1) has the constituent units (S1) and (S2), the molar ratio of the constituent units (S2) is 15 mol% or more and 85 mol% or less with respect to all the constituent units. It is more preferably 30 mol% or more and 80 mol% or less, and further preferably 35 mol% or more and 65 mol% or less.

The polyorganosylsesquioxane (a1) may have a constituent unit (S3) other than the constituent units (S1) and (S2) as long as it does not affect the effect of the present invention. In the polyorganosylsesquioxane (a1), the molar ratio of the constituent unit (S3) is preferably 10 mol% or less, more preferably 5 mol% or less, based on all the constituent units. It is more preferable that the structural unit (S3) is not included.

When the polyorganosylsesquioxane (a1) is a polymer obtained by polymerizing only one kind of monomer, the polyorganosylsesquioxane (a1) preferably has a structural unit (S1). It is more preferable to have the structural unit represented by the general formula (S1-1), and it is further preferable to have the structural unit represented by the general formula (S1-2).

Specific examples of polyorganosylsesquioxane (a1) are shown below, but the present invention is not limited thereto. In the following structural formula, "SiO _1.5 " represents a silsesquioxane unit.

From the viewpoint of improving pencil hardness, the weight average molecular weight (Mw) of polyorganosylsesquioxane (a1) in terms of standard polystyrene by gel permeation chromatography (GPC) is preferably 5000 to 1,000,000, more preferably 10,000 to 10,000. It is 1,000,000, more preferably 10,000 to 100,000.

The molecular weight dispersion (Mw / Mn) of polyorganosylsesquioxane (a1) in terms of standard polystyrene by GPC is, for example, 1.0 to 4.0, preferably 1.1 to 3.7, and more. It is preferably 1.2 to 3.0, and more preferably 1.3 to 2.5. Mw represents the weight average molecular weight and Mn represents the number average molecular weight.

The weight average molecular weight and molecular weight dispersion of polyorganosylsesquioxane (a1) are measured by the following devices and conditions.
Measuring device: Product name "LC-20AD" (manufactured by Shimadzu Corporation)
Columns: Shodex KF-801 x 2, KF-802, and KF-803 (manufactured by Showa Denko KK)
Measurement temperature: 40 ° C
Eluent: N-methylpyrrolidone (NMP), sample concentration 0.1-0.2% by mass
Flow rate: 1 mL / min Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation)
Molecular weight: Standard polystyrene conversion

<Manufacturing method of polyorganosylsesquioxane (a1)>
The method for producing polyorganosylsesquioxane (a1) is not particularly limited, and it can be produced using a known production method. For example, it can be produced by a method of hydrolyzing and condensing a hydrolyzable silane compound. .. Examples of the hydrolyzable silane compound include 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 (Sd1-1)) and a crosslinkable group. It is preferable to use a hydrolyzable trifunctional silane compound (preferably a compound represented by the following general formula (Sd2-1)).
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 above general formula (Sd2-1). It corresponds to the structural unit represented by the formula (S2-1).

In the general formula (Sd1-1), X ¹ to X ³ independently represent an alkoxy group or a halogen atom, L ₁₁ represents a substituted or unsubstituted alkylene group, and R ₁₁ represents a single bond, -NH-,-. O-, -C (= O)-, or a divalent linking group obtained by combining these, L ₁₂ represents a substituted or unsubstituted alkylene group, and Q ₁₁ represents a crosslinkable group. However, 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), X 4 ~ X}} 6 each independently represent an alkoxy group or a halogen _{atom, L 21} represents a substituted or unsubstituted alkylene _{group, Q 21} represents a crosslinkable group.

_L 11 in the general formula _{_{(Sd1-1), R 11, L}} 12, and _{Q 11} is, _L 11 in the general formula _{_{(S1-1), R 11, L}} 12, and _{Q 11} and have the same meanings, The preferred range is similar.
_{L 21,} and _{Q 21} in formula (Sd2-1) is, _{L 21} in the general formula (S2-1), and _{Q 21} and have the same meanings and preferred ranges are also the same.

Formula (Sd1-1), (Sd2-1) ^in, an alkoxy group or a halogen atom each independently ^X 1 ~ X ^6.
Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
As X ¹ to X ⁶ , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. Note that X ¹ to X ⁶ may be the same or different.

The amount and composition of the hydrolyzable silane compound used can be appropriately adjusted according to the desired structure of the polyorganosylsesquioxane (a1).

Further, the hydrolysis and condensation reactions of the hydrolyzable silane compound can be carried out simultaneously or sequentially. When the above reactions are carried out sequentially, the order in which the reactions are carried out is not particularly limited.

The hydrolysis and condensation reaction of the hydrolyzable silane compound can be carried out in the presence or absence of a solvent, and is preferably carried out in the presence of a solvent.
Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate and ethyl acetate. , Esters such as isopropyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol. And so on.
As the solvent, ketones or ethers are preferable. As the solvent, one type may be used alone, or two or more types may be used in combination.

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

The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably carried out in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkali catalyst.
The acid catalyst is not particularly limited, and for example, mineral acids such as hydrochloric acid, sulfuric acid, nitrate, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid and trifluo. Examples thereof include sulfonic acids such as lomethane sulfonic acid and p-toluene sulfonic acid; solid acids such as active white clay; and Lewis acids such as iron chloride.
The alkali catalyst is not particularly limited, and for example, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; magnesium hydroxide, calcium hydroxide, barium hydroxide and the like. Alkali earth metal hydroxides; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; alkali earth metal carbonates such as magnesium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, hydrogen carbonate Alkali metal hydrogen carbonates such as potassium and cesium hydrogen carbonate; alkali metal organic acid salts such as lithium acetate, sodium acetate, potassium acetate and cesium acetate (eg acetate); alkaline earth metal organic salts such as magnesium acetate Acetates (eg, acetates); alkali metal alkoxides such as lithium methoxyd, sodium methoxyd, sodium ethoxydo, sodium isopropoxide, potassium ethoxydo, potassium t-butoxide; alkali metal phenoxides such as sodium phenoxide; Amines such as triethylamine, N-methylpiperidin, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5-ene (tertiary) Amine and the like); Examples thereof include nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridyl and 1,10-phenanthroline.
One type of catalyst may be used alone, or two or more types may be used in combination. The catalyst can also 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 can be appropriately adjusted within the range of 0.002 to 0.200 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound.

The amount of water used in the above-mentioned hydrolysis and condensation reaction is not particularly limited, and is usually adjusted appropriately within the range of 0.5 to 40 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. it can.

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

The reaction temperature of the hydrolysis and condensation reactions is not particularly limited, and is, for example, 40 to 100 ° C, preferably 45 to 80 ° C. The reaction time of the hydrolysis and condensation reactions is not particularly limited, and is, for example, 0.1 to 15 hours, preferably 1.5 to 10 hours. Further, the hydrolysis and condensation reactions can be carried out under normal pressure, under pressure or under reduced pressure. The atmosphere for performing the hydrolysis and condensation reactions may be, for example, an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or an oxygen presence such as under air, but the inert gas may be used. The atmosphere is preferable.

Polyorganosylsesquioxane (a1) can be obtained by the hydrolysis and condensation reaction of the hydrolyzable silane compound. The catalyst may be neutralized after the completion of the hydrolysis and condensation reactions. Further, the polyorganosylsesquioxane (a1) is separated by, for example, water washing, acid washing, alkaline washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and the like, and a combination thereof. It may be separated and purified by a separation means or the like.

Only one type of polyorganosylsesquioxane (a1) may be used, or two or more types having different structures may be used in combination.
When two or more kinds of polyorganosylsesquioxane (a1) are mixed, the hydrogen bond value, side chain length, and crosslinkable base value are calculated by each numerical value (hydrogen bond value, side chain length, crosslinkable base value). ) Multiplied by the compounding ratio (mass ratio) to obtain the total value (mass average value) of the mixture.

The content of polyorganosylsesquioxane (a1) in the resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total solid content of the resin composition. It is more preferably 80% by mass or more. The upper limit of the content of polyorganosylsesquioxane (a1) in the resin composition is preferably 99.9% by mass or less, preferably 98% by mass or less, based on the total solid content of the resin composition. Is more preferable, and 97% by mass or less is further preferable.
The total solid content is all components other than the solvent.

<Polymerization initiator>
The resin composition in the present invention preferably contains a polymerization initiator.
If the crosslinkable group of the polyorganosylsesquioxane (a1) used in the resin composition is a radically polymerizable crosslinkable group, it is preferable to contain a radical polymerization initiator, and the crosslinkable group is a cationically polymerizable crosslinkable group. If it is a group, it is preferable to include a cationic polymerization initiator.
The polymerization initiator is preferably a radical polymerization initiator. The radical polymerization initiator may be either a radical photopolymerization initiator or a radical thermal polymerization initiator, but a radical photopolymerization initiator is more preferable.
Only one type of polymerization initiator may be used, or two or more types having different structures may be used in combination.

The radical photopolymerization initiator may be any one capable of generating radicals as an active species by light irradiation, and known radical photopolymerization initiators can be used without any limitation. Specific examples include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl). ) Ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2 -Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer, 2-hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] Acetphenones such as phenyl} -2-methyl-propane-1-one; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9 -Oxime esters such as -ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime); benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoyls such as benzoin isobutyl ether; benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3', 4,4'-tetra (t-butylper) Oximecarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethanamineium bromide, (4-) Benzoylbenzyl) Benzophenones such as trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethyl) Amino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-onemethochloride and other thioxanthones; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) Acids such as -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Luphosphon oxides; etc. In addition, as an auxiliary agent for the radical photopolymerization initiator, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethyl benzoic acid, 4- Ethyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoic acid (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4- Diisopropylthioxanson or the like may be used in combination.
The above radical photopolymerization initiator and auxiliary agent can be synthesized by a known method and are also available as commercial products.

The content of the polymerization initiator in the resin composition is not particularly limited, but is preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of polyorganosylsesquioxane (a1), for example. ~ 50 parts by mass is more preferable.

<Solvent>
The resin composition in the present invention may contain a solvent.
As the solvent, an organic solvent is preferable, and one kind or two or more kinds of organic solvents can be mixed and used at an arbitrary ratio. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol, and i-butanol; ketones such as acetone, methylisobutylketone, methylethylketone, and cyclohexanone; cellosolves such as ethylcellosolve; toluene. , Aromatic substances such as xylene; glycol ethers such as propylene glycol monomethyl ether; acetate esters such as methyl acetate, ethyl acetate and butyl acetate; diacetone alcohol and the like.
The content of the solvent in the resin composition in the present invention can be appropriately adjusted within a range in which the coating suitability of the resin composition can be ensured. For example, it can be 50 to 500 parts by mass, preferably 80 to 200 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition.
The resin composition usually takes the form of a liquid.
The concentration of the solid content of the resin composition is usually about 10 to 90% by mass, preferably about 20 to 80% by mass, and particularly preferably about 40 to 70% by mass.

<Other additives>
The resin composition in the present invention may contain components other than the above, and contains, 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.

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

[Hard coat film]
The present invention also relates to a hard coat film having a base material and a hard coat layer containing a cured product of the above resin composition.
The hard coat film of the present invention preferably has the hard coat layer on the base material.

<Base material>
The substrate used for the hard coat film of the present invention preferably has a transmittance in the visible light region of 70% or more, more preferably 80% or more, and further preferably 90% or more.

(polymer)
The substrate preferably contains a polymer.
As the polymer, a polymer having excellent optical transparency, mechanical strength, thermal stability and the like is preferable.

Examples of the polymer include a polycarbonate polymer, a polyester polymer such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and a styrene polymer such as polystyrene and an acrylonitrile-styrene copolymer (AS resin). In addition, polyolefins such as polyethylene and polypropylene, norbornene resins, polyolefin polymers such as ethylene / propylene copolymers, (meth) acrylic polymers such as polymethylmethacrylate, vinyl chloride polymers, nylon, and amides such as aromatic polyamides. Polymers, imide polymers, sulfone polymers, polyether sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinylidene chloride polymers, vinyl alcohol polymers, vinyl butyral polymers, allylate polymers, polyoxy Examples thereof include methylene-based polymers, epoxy-based polymers, cellulose-based polymers typified by triacetyl cellulose, copolymers of the above polymers, and polymers in which the above polymers are mixed.

In particular, amide-based polymers such as aromatic polyamides and imide-based polymers have a large number of breaks and bends measured by a MIT tester in accordance with JIS (Japanese Industrial Standards) P8115 (2001) and have a relatively high hardness. It can be preferably used. For example, it is preferable to use the aromatic polyamide as described in Example 1 of Japanese Patent No. 56994454, the polyimides described in JP-A-2015-508345, JP-A-2016-521216, and WO2017 / 014287 as a base material. Can be used.
As the amide-based polymer, aromatic polyamide (aramid-based polymer) is preferable.
The base material preferably contains at least one polymer selected from imide-based polymers and aramid-based polymers.

Further, the base material can be formed as a cured layer of an ultraviolet curable type or thermosetting type resin such as acrylic type, urethane type, acrylic urethane type, epoxy type and silicone type.

(Flexible material)
The base material may contain a material that further softens the above polymer. The softening material refers to a compound that improves the number of fractures and bends, and as the softening material, a rubber elastic body, a brittleness improver, a plasticizer, a slide ring polymer, or the like can be used.
Specifically, as the softening material, the softening material described in paragraph numbers [0051] to [0114] in JP-A-2016-167043 can be preferably used.

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

The amount of these softening materials to be mixed is not particularly limited, and a polymer having a sufficient number of breaks and bends may be used alone as a base material for the film, or the softening materials may be mixed, or all of them. May be used as a softening material (100%) to have a sufficient number of breaks and bends.

(Other additives)
Various additives (for example, ultraviolet absorbers, matting agents, antioxidants, peeling accelerators, retardation (optical anisotropy) adjusting agents, etc.) can be added to the base material depending on the application. They may be solid or oily. That is, the melting point or boiling point is not particularly limited. Further, the additive may be added at any time in the step of producing the base material, or the step of adding the additive and preparing may be added to the material preparation step. Furthermore, the amount of each material added is not particularly limited as long as the function is exhibited.
As other additives, the additives described in paragraph numbers [0117] to [0122] in JP-A-2016-167043 can be preferably used.

One type of the above additives may be used alone, or two or more types may be used in combination.

(UV absorber)
Examples of the ultraviolet absorber include a benzotriazole compound, a triazine compound, and a benzoxazine compound. Here, 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 JP2013-1111835. The triazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based ultraviolet absorbers described in paragraph 0033 of JP2013-1111835. As the benzoxazine compound, for example, those described in paragraph 0031 of JP-A-2014-209162 can be used. The content of the ultraviolet absorber in the base material is, for example, 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, regarding the ultraviolet absorber, reference is also made to paragraph 0032 of JP2013-1111835. In the present invention, an ultraviolet absorber having high heat resistance and low volatilization is preferable. Examples of such an ultraviolet absorber include UVSORB101 (manufactured by Fujifilm Fine Chemicals Co., Ltd.), TINUVIN 360, TINUVIN 460, TINUVIN 1577 (manufactured by BASF), LA-F70, LA-31, LA-46 (manufactured by ADEKA) and the like. Can be mentioned.

From the viewpoint of transparency, it is preferable that the base material has a small difference in refractive index between the flexible material and various additives used for the base material and the polymer.

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

G in the formula (PI) represents a tetravalent organic group, and A represents a divalent organic group. G ² in the formula (a) represents a trivalent organic group, and A ² represents a divalent organic group. G ³ in the formula (a') represents a tetravalent organic group, and A ³ represents a divalent organic group. ^{G 4} and ^{A 4} in the formula (b) represents each a divalent organic group.

In the formula (PI), the organic group of the tetravalent organic group represented by G (hereinafter, may be referred to as the organic group of G) includes an acyclic aliphatic group, a cyclic aliphatic group and an aromatic group. Examples are groups selected from the group consisting of. The organic group of G is preferably a tetravalent cyclic aliphatic group or a tetravalent aromatic group from the viewpoint of transparency and flexibility of the base material containing the imide polymer. The aromatic group includes a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings in which they are directly or linked to each other by a bonding group. And so on. From the viewpoint of transparency of the base material and suppression of coloring, the organic group of G is a cyclic aliphatic group, a cyclic aliphatic group having a fluorine-based substituent, a monocyclic aromatic group having a fluorine-based substituent, and the like. It is preferably 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, the fluorine-based substituent means a group containing a fluorine atom. The fluorine-based substituent is preferably a fluoro group (fluorine atom, −F) and a perfluoroalkyl group, and more preferably a fluoro group and a trifluoromethyl group.

More specifically, the organic group of G is, 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 heteroalkylaryl. It is selected from groups that have a group and any two of these (which may be the same) and which are linked to each other directly or by a binding group. Examples of the bonding group include -O-, an alkylene group having 1 to 10 carbon atoms, -SO _2- , -CO- or -CO-NR- (R is a methyl group, an ethyl group, a propyl group and the like having 1 to 1 carbon atoms. (Representing an alkyl group of 3 or a hydrogen atom).

The tetravalent organic group represented by G usually has 2 to 32 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms. When the organic group of G is a cyclic aliphatic group or an aromatic group, at least one of the carbon atoms constituting these groups may be replaced with a heteroatom. Heteroatoms include O, N or S.

Specific examples of G include groups represented by the following equations (20), (21), (22), (23), (24), (25) or (26). Be done. * In the formula indicates a bond. Z in formula (26) is a single bond, -O-, -CH _2- , -C (CH ₃ ) _2- , -Ar-O-Ar-, -Ar-CH ₂ -Ar-, -Ar- Represents C (CH ₃ ) _2- Ar- or -Ar-SO _2- Ar-. Ar represents an aryl group having 6 to 20 carbon atoms, and may be, for example, a phenylene group. At least one of the hydrogen atoms of these groups may be substituted with a fluorine-based substituent.

In the formula (PI), the organic group of the divalent organic group represented by A (hereinafter, may be referred to as the organic group of A) includes an acyclic aliphatic group, a cyclic aliphatic group and an aromatic group. Examples include groups selected from the group consisting of. The divalent organic group represented by A is preferably selected from a divalent cyclic aliphatic group and a divalent aromatic group. Aromatic groups include monocyclic aromatic groups, fused polycyclic aromatic groups, and non-condensed polycyclic aromatics having two or more aromatic rings, which are directly or interconnected by a bonding group. The group is mentioned. From the viewpoint of transparency of the base material and suppression of coloring, it is preferable that a fluorine-based substituent is introduced into the organic group of A.

More specifically, the organic group of A is, 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 heteroalkylaryl. It is selected from groups that have a group and any two of these (which may be the same) and to which they are linked directly or by a binding group. Examples of the heteroatom include O, N or S, and examples of the bonding group are -O-, an alkylene group having 1 to 10 carbon atoms, -SO _2- , -CO- or -CO-NR- (R is methyl). An alkyl group having 1 to 3 carbon atoms such as a group, an ethyl group, and a propyl group, or a hydrogen atom) can be mentioned.

The number of carbon atoms of the divalent 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 groups represented by the following formulas (30), formulas (31), formulas (32), formulas (33) or formulas (34). * In the formula indicates a bond. Z ¹ to Z ³ are independently single-bonded, -O-, -CH _2- , -C (CH ₃ ) _2- , -SO _2- , -CO- or -CO-NR- (R is Represents an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group, or a hydrogen atom). In the following groups, Z ¹ and Z ² and Z ² and Z ³ are preferably in the meta or para position with respect to each ring, respectively. Further, it is preferable that the single bond between Z ¹ and the terminal, the single bond between Z ² and the terminal, and the single bond between Z ³ and the terminal are in the meta position or the para position, respectively. In one example of A, Z ¹ and Z ³ are -O- and Z ² is -CH _2- , -C (CH ₃ ) _2- or -SO _2- . One or more of the hydrogen atoms of these groups may be substituted with fluorine-based substituents.

At least one hydrogen atom among the hydrogen atoms constituting at least one of A and G is 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. It may be substituted with a functional group. Further, when the organic group of A and the organic group of G are cyclic aliphatic groups or aromatic groups, respectively, it is preferable that at least one of A and G has a fluorine-based substituent, and both A and G have a fluorine-based substituent. It is more preferable to have a fluorine-based substituent.

G ² in the formula (a) is a trivalent organic group. This organic group can be selected from the same groups as the organic group of G in the formula (PI) except that it is a trivalent group. As an example of G ² , a group in which any one of the four bonds of the groups represented by the formulas (20) to (26) given as a specific example of G is replaced with a hydrogen atom is mentioned. Can be done. A ² in formula (a) can be selected from the same groups as A in formula (PI).

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

^{G 4} in formula (b) is a divalent organic group. This organic group can be selected from the same groups as the organic group of G in the formula (PI) except that it is a divalent group. An example of G ⁴ is a group in which any two of the four bonds of the groups represented by the formulas (20) to (26) given as specific examples of G are replaced with hydrogen atoms. Can be done. A ⁴ in the formula (b) may be selected from the same groups as A in the formula (PI).

The imide-based polymer contained in the base material containing the imide-based polymer includes diamines and a tetracarboxylic acid compound (including a tetracarboxylic acid compound analog such as an acid chloride compound and a tetracarboxylic acid dianhydride) or a tricarboxylic acid compound (a tricarboxylic acid compound) It may be a condensed polymer obtained by polycondensing with at least one of (including an acid chloride compound and a tricarboxylic acid compound analog such as tricarboxylic acid anhydride). Further, a dicarboxylic acid compound (including an analog such as an acid chloride compound) may be polycondensed. The repeating structural unit represented by the formula (PI) or the formula (a') is usually derived from diamines and tetracarboxylic acid compounds. The repeating structural unit represented by the formula (a) is usually derived from diamines and tricarboxylic acid compounds. The repeating structural unit represented by the formula (b) is usually derived from diamines and dicarboxylic acid compounds.

Examples of the tetracarboxylic acid compound include an aromatic tetracarboxylic acid compound, an alicyclic tetracarboxylic acid compound, and an acyclic aliphatic tetracarboxylic acid compound. These may be used in combination of two 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 may be an alicyclic tetracarboxylic acid compound, an aromatic tetracarboxylic acid compound, or the like from the viewpoint of solubility of the imide-based polymer in a solvent and transparency and flexibility when a base material is formed. preferable. From the viewpoint of transparency and suppression of coloring of the substrate containing the imide-based polymer, the tetracarboxylic acid compound is an alicyclic tetracarboxylic acid compound having a fluorine-based substituent and an aromatic tetracarboxylic acid compound having a fluorine-based substituent. It is preferably selected from, and more preferably an alicyclic tetracarboxylic acid compound having a fluorine-based substituent.

Examples of the tricarboxylic acid compound include aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids, acid chloride compounds related thereto, acid anhydrides and the like. The tricarboxylic acid compound is preferably selected from aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids and related acid chloride compounds thereof. Two or more kinds of tricarboxylic acid compounds may be used in combination.

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

Examples of the dicarboxylic acid compound include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, acid chloride compounds related thereto, acid anhydrides and the like. The dicarboxylic acid compound is preferably selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids and related acid chloride compounds thereof. Two or more kinds of dicarboxylic acid compounds may be used in combination.

The dicarboxylic acid compound is an alicyclic dicarboxylic acid compound or an aromatic dicarboxylic acid compound from the viewpoint of the solubility of the imide-based polymer in a solvent and the transparency and flexibility when a substrate containing the imide-based polymer is formed. Is preferable. From the viewpoint of transparency and suppression of coloring of the base material containing the imide-based polymer, the dicarboxylic acid compound shall be an alicyclic dicarboxylic acid compound having a fluorine-based substituent or an aromatic dicarboxylic acid compound having a fluorine-based substituent. Is even more preferable.

Examples of diamines include aromatic diamines, alicyclic diamines and aliphatic diamines, and two or more of these may be used in combination. From the viewpoint of the solubility of the imide polymer in the solvent and the transparency and flexibility when the base material containing the imide polymer is formed, the diamines are selected from alicyclic diamines and aromatic diamines having a fluorine-based substituent. It is preferable to be selected.

When such an imide polymer is used, it has particularly excellent flexibility, high light transmittance (for example, 85% or more, preferably 88% or more with respect to light at 550 nm), and low yellowness (YI value). It is easy to obtain a substrate having 5, 5 or less, preferably 3 or less), and a low haze (1.5% or less, preferably 1.0% or less).

The imide-based polymer may be a copolymer containing a plurality of different types 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-based polymer is large, high flexibility tends to be easily obtained, but if the weight average molecular weight of the imide-based polymer is too large, the viscosity of the varnish tends to be high and the processability tends to be lowered.

The imide-based polymer may contain a halogen atom such as a fluorine atom that can be introduced by the above-mentioned fluorine-based substituent or the like. When the polyimide polymer contains a halogen atom, the elastic modulus of the base material containing the imide polymer can be improved and the yellowness can be reduced. As a result, scratches and wrinkles generated on the hard coat film can be suppressed, and the transparency of the base material containing the imide polymer can be improved. The halogen atom is preferably a fluorine atom. The content of halogen atoms in the polyimide-based polymer is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, based on the mass of the polyimide-based polymer.

The base material containing the imide-based polymer may contain one kind or two or more kinds of ultraviolet absorbers. The ultraviolet absorber can be appropriately selected from those usually used as an ultraviolet absorber in the field of resin materials. The ultraviolet absorber may contain a compound that absorbs light having a wavelength of 400 nm 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 "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 a benzophenone as a maternal skeleton and a substituent attached to the benzophenone.

The content of the ultraviolet absorber is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and usually 10% by mass or less, based on the total mass of the base material. Yes, preferably 8% by mass or less, and more preferably 6% by mass or less. By including the ultraviolet absorber in these amounts, the weather resistance of the base material can be enhanced.

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

Examples of the silicon material containing a silicon atom include silica particles, a 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 base material containing the imide polymer.

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

The average primary particle size of the silica particles in the substrate containing the imide polymer can be determined by observation with a transmission electron microscope (TEM). The primary particle diameter of the silica particles can be a directional diameter measured by a transmission electron microscope (TEM). The average primary particle size can be obtained by measuring 10 points of the primary particle size by TEM observation and as an average value thereof. The particle distribution of the silica particles before forming the base material containing the imide-based polymer can be obtained by a commercially available laser diffraction type particle size distribution meter.

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

The base material containing the imide polymer may further contain components other than the imide polymer and the inorganic material as long as the transparency and flexibility are not significantly impaired. Examples of components other than the imide polymer and the inorganic material include colorants such as antioxidants, mold release agents, stabilizers and bluing agents, flame retardants, lubricants, thickeners and leveling agents. The ratio of the components other than the imide polymer and 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 with respect to the mass of the base material. ..

When the base material containing the imide-based polymer contains the imide-based polymer and the silicon material, it is preferable that Si / N, which is the ratio of the number of atoms of the silicon atom to the nitrogen atom on at least one surface, is 8 or more. The atomic number ratio Si / N is determined by evaluating the composition of the base material containing an imide-based polymer by X-ray Photoelectron Spectroscopy (XPS), and the abundance of silicon atoms and nitrogen atoms obtained thereby. It is a value calculated from the abundance of.

When the Si / N on at least one surface of the substrate containing the imide-based polymer is 8 or more, sufficient adhesion to the hard coat layer can be obtained. From the viewpoint of adhesion, the 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 base material)
The base material is preferably in the form of a film.
The thickness of the base material is more preferably 100 μm or less, further preferably 80 μm or less, and most preferably 50 μm or less. When the thickness of the base material is reduced, the difference in curvature between the front surface and the back surface at the time of bending becomes small, cracks and the like are less likely to occur, and the base material is not broken even when bent a plurality of times. On the other hand, from the viewpoint of ease of handling of the base material, the thickness of the base material is preferably 3 μm or more, more preferably 5 μm or more, and most preferably 15 μm or more.

(Method of producing base material)
The substrate may be formed by thermally melting a thermoplastic polymer to form a film, or may be formed from a solution in which the polymer is uniformly dissolved by a solution film forming (solvent casting method). In the case of heat melting film formation, the above-mentioned softening material and various additives can be added at the time of heat melting. On the other hand, when the base material is prepared by the solution film forming method, the above-mentioned softening material and various additives can be added to the polymer solution (hereinafter, also referred to as dope) in each preparation step. Further, the timing of addition may be any in the dope preparation step, but the step of adding and preparing the additive may be added to the final preparation step of the dope preparation step.

The coating film may be heated for drying and / or baking of the coating film. The heating temperature of the coating film is usually 50 to 350 ° C. The coating film may be heated under an inert atmosphere or under reduced pressure. The solvent can be evaporated and removed by heating the coating film. The base material may be formed by a method including a step of drying the coating film at 50 to 150 ° C. and a step of baking the dried coating film at 180 to 350 ° C.

Surface treatment may be applied to at least one surface of the base material.

<Hard coat layer>
The hard coat film of the present invention has a hard coat layer containing a cured product of the above resin composition.
The hard coat layer is preferably formed on at least one surface of the substrate.
When the hard coat film of the present invention has a scratch resistant layer described later, it is preferable to have at least one hard coat layer between the base material and the scratch resistant layer.

(Cured product of resin composition)
The hard coat layer of the hard coat film of the present invention contains a cured product of a resin composition containing polyorganosylsesquioxane (a1), and preferably polyorganosylsesquioxane (a1) and polymerization initiation. It contains a cured product of a resin composition containing an agent.
The cured product of the resin composition preferably contains at least a cured product formed by bonding the crosslinkable groups of polyorganosylsesquioxane (a1) by a polymerization reaction.
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 70% by mass or more. It is more preferable to have.

(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 even more preferably 2 to 20 μm.
The film thickness of the hard coat layer is calculated by observing the cross section of the hard coat film with an optical microscope. The cross-section sample can be prepared by a microtome method using a cross-section cutting device Ultra Microtome, a cross-section processing method using a focused ion beam (FIB) device, or the like.

<Scratch resistant layer>
The hard coat film of the present invention preferably further has a scratch resistant layer.
When the hard coat film of the present invention has a scratch resistant layer, it is preferable to have at least one scratch resistant layer on the surface opposite to the base material of the hard coat layer.
The scratch-resistant layer of the hard coat film of the present invention preferably contains a cured product of a composition for forming a scratch-resistant layer containing a radically polymerizable compound (c1).

(Radical polymerizable compound (c1))
The radically polymerizable compound (c1) (also referred to as “compound (c1)”) will be described.
Compound (c1) is a compound having a radically polymerizable group.
The radically polymerizable group in the compound (c1) is not particularly limited, and a generally known radically polymerizable group can be used. Examples of the radically polymerizable group include a polymerizable unsaturated group, and specific examples thereof include a (meth) acryloyl group, a vinyl group, and an allyl group, and a (meth) acryloyl group is preferable. In addition, each group mentioned above may have a substituent.
The compound (c1) is preferably a compound having two or more (meth) acryloyl groups in one molecule, and more preferably a compound having three or more (meth) acryloyl groups in one 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 above compound (c1) are shown below, but the present invention is not limited thereto.
Examples of the compound having two (meth) acryloyl groups in one molecule include neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene. Glycoldi (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, polyethylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( Preferable examples thereof include meta) acrylate and dicyclopentanyldi (meth) acrylate.
Examples of the compound having three or more (meth) acryloyl groups in one molecule include esters of a polyhydric alcohol and (meth) acrylic acid. Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta. Elythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexa (meth) acrylate, etc. can be mentioned, but in terms of high cross-linking, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, or a mixture thereof is preferable.

Only one type of compound (c1) may be used, or two or more types having different structures may be used in combination.

The content of the compound (c1) in the scratch-resistant layer forming composition is preferably 80% by mass or more, more preferably 85% by mass or more, based on the total solid content in the scratch-resistant layer forming composition. It is preferable, and 90% by mass or more is more preferable.

(Radical polymerization initiator)
The scratch-resistant layer-forming composition in the present invention preferably contains a radical polymerization initiator.
Only one type of radical polymerization initiator may be used, or two or more types having different structures may be used in combination. Further, 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, but is preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of the compound (c1), for example. ~ 50 parts by mass is more preferable.

(solvent)
The scratch-resistant layer-forming composition in the present invention may contain a solvent.
The solvent is the same as the solvent that may be contained in the above-mentioned resin composition.
The content of the solvent in the scratch-resistant layer-forming composition in the present invention can be appropriately adjusted within a range in which the coating suitability of the scratch-resistant layer-forming composition can be ensured. For example, it can be 50 to 500 parts by mass, preferably 80 to 200 parts by mass with respect to 100 parts by mass of the total solid content of the scratch-resistant layer forming composition.
The scratch-resistant layer-forming composition usually takes the form of a liquid.
The concentration of the solid content of the scratch-resistant layer forming composition is usually about 10 to 90% by mass, preferably about 20 to 80% by mass, and particularly preferably about 40 to 70% by mass.

(Other additives)
The scratch-resistant layer forming composition may contain components other than the above, and may contain, for example, inorganic particles, a leveling agent, an antifouling agent, an antistatic agent, a slip agent, a solvent and the like.
In particular, it is preferable to contain the following fluorine-containing compound as a slip agent.

[Fluorine-containing compound]
The fluorine-containing compound may be a monomer, an oligomer, or a polymer. The fluorine-containing compound preferably has a substituent that contributes to bond formation or compatibility with the compound (c1) in the scratch-resistant layer. The substituents may be the same or different, and it is preferable that there are a plurality of the substituents.
The substituent is preferably a polymerizable group, and may be a polymerizable reactive group exhibiting any one of radical polymerizable, cationically polymerizable, anionic polymerizable, contractile polymerizable and addition polymerizable, as an example of a preferable substituent. Examples include acryloyl group, methacryloyl group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group and amino group. Among them, a radically polymerizable group is preferable, and an acryloyl group and a methacryloyl group are particularly preferable.
The fluorine-containing compound may be a polymer or an oligomer with a compound containing no fluorine atom.

The fluorine-containing compound is preferably a fluorine-based compound represented by the following general formula (F).
General formula (F): (R ^f )-[(W)-( ^RA ) _nf ] _mf
(In the formula, R ^f represents a (per) fluoroalkyl group or (per) fluoropolyether group, W represents a single bond or a linking group, ^RA represents a polymerizable unsaturated group, and nf represents an integer of 1 to 3. .Mf represents an integer of 1 to 3.)

In the general formula (F), ^RA represents a polymerizable unsaturated group. The polymerizable unsaturated group is preferably a group having an unsaturated bond (that is, a radically polymerizable group) capable of causing a radical polymerization reaction by irradiating with an active energy ray such as an ultraviolet ray or an electron beam, and (meth). Examples include acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, etc., (meth) acryloyl group, (meth) acryloyloxy group, and a group in which any hydrogen atom in these groups is substituted with a fluorine atom. Is preferably used.

In the general formula (F), R ^f represents 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 is at least one of a fluoropolyether group and a perfluoropolyether group. Represents a species. From the viewpoint of scratch resistance, it is preferable that the fluorine content in R ^f is high.

The (par) fluoroalkyl group is preferably a group having 1 to 20 carbon atoms, and more preferably a group having 1 to 10 carbon atoms.
The (par) fluoroalkyl group has a linear structure (for example, -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, -CH ₂ (CF ₂ ) ₈ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₄ Even if it is H), it has a branched structure (for example, -CH (CF ₃ ) ₂ , -CH ₂ CF (CF ₃ ) ₂ , -CH (CH ₃ ) CF ₂ CF ₃ , -CH (CH ₃ ) (CF ₂ ). ₅ even CF 2 _H), alicyclic structure (preferably a 5- or 6-membered ring, for example perfluoro hexyl group, and a perfluorocyclopentyl group to cycloalkyl and alkyl groups substituted with these groups) There may be.

The (per) fluoropolyether group refers to a case where the (per) fluoroalkyl group has an ether bond, and may be a monovalent group or a divalent or higher valent group. Examples of the fluoropolyether group include -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , and -CH ₂ CH _2. Examples thereof include OCF ₂ CF ₂ OCF ₂ CF ₂ H, a fluorocycloalkyl group having 4 or more carbon atoms and 4 to 20 carbon atoms. Examples of the perfluoropolyether group _include- (CF ₂ O) _pf- (CF ₂ CF ₂ O) _qf -,-[CF (CF ₃ ) CF ₂ O] _pf- [CF (CF ₃ )]. _qf −, − (CF ₂ CF ₂ CF ₂ O) _pf −, − (CF ₂ CF ₂ O) _pf − and the like can be mentioned.
The pf and qf independently represent an integer of 0 to 20. However, 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 even more preferably 5 to 23.
From the viewpoint of excellent scratch resistance, the fluorine-containing compound particularly preferably has a perfluoropolyether group represented by − (CF ₂ O) _pf − (CF ₂ CF ₂ O) _qf −.

In the present invention, it is preferable that the fluorine-containing compound 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 an alkylene group, an arylene group and a heteroalkylene group, and a linking group in which these groups are combined. These linking groups may further have an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, etc., and a functional group in which these groups are combined.
The W is preferably an ethylene group, 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 even more preferably 40 to 70% by mass.

Examples of preferable fluorine-containing compounds include R-2020, M-2020, R-3833, M-3833 and Optool DAC (trade name) manufactured by Daikin Chemical Corporation, and Megafuck F-171 manufactured by DIC Corporation. , F-172, F-179A, RS-78, RS-90, Defenser MCF-300 and MCF-323 (hereinafter referred to as trade names), but are not limited thereto.

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

The weight average molecular weight (Mw) of a fluorine-containing compound having a polymerizable unsaturated group can be measured by using molecular exclusion chromatography, for example, gel permeation chromatography (GPC).
The Mw of the fluorine-containing compound used in the present invention is preferably 400 or more and less than 50,000, more preferably 400 or more and less than 30,000, and further preferably 400 or more and less than 25,000.

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

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

(Cured product of scratch resistant layer forming composition)
The scratch-resistant layer of the hard coat film of the present invention preferably contains a cured product of the composition for forming a scratch-resistant layer containing the compound (c1), and more preferably contains the compound (c1) and a radical polymerization initiator. It contains a cured product of a scratch-resistant layer-forming composition.
The cured product of the scratch-resistant layer forming composition preferably contains at least a cured product obtained by polymerizing the radically polymerizable group of the compound (c1).
The content of the cured product of the scratch-resistant layer-forming composition in the scratch-resistant layer of the hard coat film of the present invention is preferably 60% by mass or more, preferably 70% by mass or more, based on the total mass of the scratch-resistant layer. More preferably, 80% by mass or more is further preferable.

(Thickness of scratch resistant layer)
The film thickness of the scratch-resistant layer is preferably less than 3.0 μm, more preferably 0.1 to 2.0 μm, and preferably 0.1 to 1.0 μm from the viewpoint of repeated bending resistance. More preferred.

<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, and more preferably 4H or more.
Pencil hardness can be evaluated according to JIS (JIS is Japanese Industrial Standards (Japanese Industrial Standards)) K5400.

<Repeat bending resistance>
The hard coat film of the present invention has excellent repeated bending resistance.
It is preferable that the hard coat film of the present invention does not crack when the 180 ° bending test is repeated 100,000 times with a radius of curvature of 2 mm with the base material inside.
The repeated bending resistance is specifically measured as follows.
A sample film having a width of 15 mm and a length of 150 mm is cut out from the hard coat film and allowed to stand at a temperature of 25 ° C. and a relative humidity of 65% for 1 hour or more. Then, using a 180 ° folding resistance tester (IMC-0755 type manufactured by Imoto Seisakusho Co., Ltd.), the bending resistance is repeatedly tested with the base material inside. The above-mentioned tester bends the sample film along the curved surface of a rod (cylinder) having a diameter of 4 mm at a bending angle of 180 ° at the central portion in the longitudinal direction, and then returns it to its original position (spreads the sample film) once. This test is repeated. It is visually evaluated whether or not cracks occur when the above 180 ° bending test is repeated.

A hard coat film having a base material and a hard coat layer in this order, wherein the hard coat layer contains a cured product of a resin composition containing the above-mentioned polyorganosylsesquioxane (a1). By doing so, it is possible to obtain a hard coat film having excellent resistance to repeated bending and pencil hardness.

As the hard coat film, a hard coat film having a pencil hardness of 3H or more and having the above base material inside and having a radius of curvature of 2 mm and a 180 ° bending test repeated 100,000 times is preferable.

<Manufacturing method of hard coat film>
The method for producing the hard coat film of the present invention will be described.
The method for producing the hard coat film of the present invention is preferably a production method including the following steps (I) and (II). When the hard coat film has a scratch resistant layer, it is preferable that the production method further includes the following steps (III) and (IV).
(I) Step of applying a resin composition containing polyorganosylsesquioxane (a1) on a base material to form a hard coat layer coating film (II) Hard by curing the above hard coat layer coating film. Step of forming a coat layer (III) A step of applying a scratch-resistant layer-forming composition containing a radically polymerizable compound (c1) onto the hard coat layer to form a scratch-resistant layer coating film (IV). Scratch layer A process of forming a scratch resistant layer by curing the coating film

-Step (I)-
Step (I) is a step of applying a resin composition containing polyorganosylsesquioxane (a1) on a base material to provide a hard coat layer coating film.
The base material, polyorganosylsesquioxane (a1), and resin composition are as described above.

The method for applying the resin composition is not particularly limited, and a known method can be used. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method and the like can be mentioned.

-Step (II)-
Step (II) is a step of forming a hard coat layer by curing the hard coat layer coating film. Curing the hard coat layer coating means polymerizing at least a part of the crosslinkable groups of polyorganosylsesquioxane (a1) contained in the hard coat layer coating.

The hardening of the hard coat layer coating film is preferably performed by irradiation with ionizing radiation or heating.

The type of ionizing radiation is not particularly limited, and examples thereof include X-rays, electron beams, ultraviolet rays, visible light, and infrared rays, but ultraviolet rays are preferably used. For example, if the hard coat layer coating film is ultraviolet curable, it is preferable to irradiate an ultraviolet lamp with an irradiation amount of 10 mJ / cm ² to 2000 mJ / cm ² to cure the curable compound, and the hard coat film is hard. When a scratch-resistant layer is provided on the coat layer, it is preferable to semi-cure the curable compound. More preferably ^{50mJ / cm 2 ~ 1800mJ / cm} 2, further preferably 100mJ / cm 2 ~ 1500mJ / cm 2. As the ultraviolet lamp type, a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used.

When curing by heat, the temperature is not particularly limited, but is preferably 80 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 180 ° C. or lower, and further preferably 120 ° C. or higher and 160 ° C. or lower. preferable.

The oxygen concentration at the time of curing is preferably 0 to 1.0% by volume, more preferably 0 to 0.1% by volume, and most preferably 0 to 0.05% by volume.

-Step (III)-
The step (III) is a step of applying a scratch-resistant layer forming composition containing a radically polymerizable compound (c1) onto the hard coat layer to form a scratch-resistant layer coating film.
The radically 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. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method and the like can be mentioned.

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

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

In the present invention, when the hard coat film has a scratch resistant layer on the hard coat layer, it is preferable to semi-cure the hard coat layer coating film in the above step (II). That is, in the step (II), the hard coat layer coating film is semi-cured, and then in the step (III), the scratch resistant layer forming composition is applied onto the semi-cured hard coat layer to apply the scratch resistant layer coating film. Then, in step (IV), it is preferable to cure the scratch-resistant layer coating film and completely cure the hard coat layer. Here, semi-curing the hard coat layer coating film means polymerizing only a part of the crosslinkable groups of polyorganosylsesquioxane (a1) contained in the hard coat layer coating film. Semi-curing of the hard coat layer coating film can be performed by adjusting the irradiation amount of ionizing radiation and the temperature and time of heating.

Drying treatment as needed between steps (I) and step (II), between steps (II) and step (III), between steps (III) and step (IV), or after step (IV) May be done. The drying process is performed by blowing warm air, arranging in a heating furnace, transporting in a heating furnace, heating with a roller from a surface (base material surface) not provided with a hard coat layer and a scratch resistant layer, and the like. be able to. The heating temperature may be set to a temperature at which the solvent can be dried and removed, and is not particularly limited. Here, the heating temperature means 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 of an image display device, and can be used, for example, as a surface protective film of a foldable device (foldable display). A foldable device is a device that employs a flexible display whose display screen can be deformed, and the device body (display) can be folded by utilizing the deformability of the display screen.
Examples of the foldable device include an organic electroluminescence device and the like.

The present invention is a polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The hydrogen bond value is 3.0 or more, the side chain length is 14 × 10 ^-10 to 19 × 10 ^-10 m, and the side chain length is 14 × 10 ^-10 to 19 × 10 ^-10 m.
The hydrogen bond value is represented by the following formula (1), and the side chain length is a polyorganosylsesquioxane in which the side chain length represents the length from the Si atom to the end of the side chain. Also involved.

Further, the present invention is a polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The hydrogen bond value is 3.0 or more, the crosslinkable base value is 4.5 to 6.0, and
The hydrogen bond value is represented by the following formula (1), and the crosslinkable base value is also related to polyorganosylsesquioxane represented by the following formula (5).

The polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond is the same as the polyorganosylsesquioxane (a1) having a group containing a hydrogen atom capable of forming a hydrogen bond in the above resin composition. The same applies to the preferable range.
The hydrogen bond value, side chain length, and crosslinkable base value are the same as the hydrogen bond value, side chain length, and crosslinkable base value described in the above resin composition, respectively, and the preferable ranges are also the same.
In the above polyorganosylsesquioxane, the hydrogen bond value is 3.0 or more, the side chain length is 14 × ^10-10 to 19 × ^10-10 m, and the crosslinkable base value is 4.5 to 6. It is preferably 0.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not construed as being limited thereto.

<Preparation of base material>
(Manufacturing of polyimide powder)
After adding 832 g of N, N-dimethylacetamide (DMAc) under a nitrogen stream to a 1 L reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature controller and cooler, the temperature of the reactor was changed to 25. It was set to ° C. To this, 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was added and dissolved. While maintaining the obtained solution at 25 ° C., 31.09 g (0.07 mol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and biphenyltetracarboxylic dianhydride were added. 8.83 g (0.03 mol) of a substance (BPDA) was added, and the mixture was stirred for a certain period of time to react. Then, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution having a solid content concentration of 13% by mass. Next, 25.6 g of pyridine and 33.1 g of acetic anhydride were added to this polyamic acid solution and stirred for 30 minutes, further stirred at 70 ° C. for 1 hour, and then cooled to room temperature. 20 L of methanol was added thereto, and the precipitated solid content was filtered and pulverized. Then, it was dried in a vacuum at 100 degreeC for 6 hours to obtain 111 g of polyimide powder.

(Preparation of base material S-1)
100 g of the polyimide powder was dissolved in 670 g of N, N-dimethylacetamide (DMAc) to obtain a 13 mass% solution. The obtained solution was poured on a stainless steel plate and dried with hot air at 130 ° C. for 30 minutes. After that, the film is peeled off from the stainless steel plate, fixed to the frame with a pin, the frame to which the film is fixed is placed in a vacuum oven, heated for 2 hours while gradually increasing the heating temperature from 100 ° C to 300 ° C, and then gradually. Cooled to. After separating the cooled film from the frame, as a final heat treatment step, the film was further heat-treated at 300 ° C. for 30 minutes to obtain a substrate S-1 having a thickness of 30 μm and made of a polyimide film.

<Synthesis of polyorganosylsesquioxane (SQ1-1)>
300 mmol (53.8 g) of 3-aminopropyltrimethoxysilane and 166 g of methyl isobutyl ketone were mixed, and the solution was cooled to 5 ° C. or lower. To the cooled solution, 300 mmol (42.3 g) of 2-acryloyloxyethyl isocyanate was added dropwise, and the temperature was raised to room temperature after the reaction.
Then, a mixture of 300 mmol (70.3 g) of 3- (trimethoxysilyl) propyl acrylate, 7.39 g of triethylamine, and 434 g of acetone was added to the above solution, and 73.9 g of pure water was further added using a dropping funnel. Then, the mixture was added dropwise over 30 minutes and then heated to 50 ° C., and a polycondensation reaction was carried out for 10 hours.
Then, the reaction solution was cooled, neutralized with 12 mL of a 1N (mol / L) hydrochloric acid aqueous solution, 600 g of 1-methoxy-2-propanol was added, and then concentrated under the conditions of 30 mmHg and 50 ° C., and the solid content concentration was 30% by mass. Polyorganosyl sesquioxane (SQ1-1), which is a clear liquid product, was obtained as a 2-methoxy-1-propanol solution of.

5 mg of the polymer obtained above was dissolved in 0.5 mL of deuterated chloroform and measured at BRUKER AVANCE III HD 400 MHz (manufactured by Hitachi High-Tech Science Corporation). The results are shown below.
^{1 1} H NMR (400 MHz, CDCl ₃ , ppm): δ6.3-6.5 (d, acrylic part CH ₂ = CHCO ₂ ), δ6.0-6.2 (m, acrylic part CH ₂ = CHCO ₂ ), δ5.8-5.9 (m, acrylic part CH ₂ = CHCO ₂ ), δ4.0-4.3 (m, CH ₂ next to acrylic part = CHCO ₂ CH ₂ , NH of urea part), δ2.8 -3.6 (m, CH ₂ next to urea part), δ1.4-1.8 (m, CH ₂ next to silyl part), δ0.4-0.8 (m, methylene part CH ₂ CH ₂ CH ₂ Si).

In the synthesis of the polyorganosylsesquioxane (SQ1-1), the content of each structural unit is the same as in the synthesis of the polyorganosylsesquioxane (SQ1-1) except that the amount of each monomer used is changed. Polyorganosilsesquioxane (SQ1-2) with a modified molar ratio was synthesized.

In the synthesis of polyorganosylsesquioxane (SQ1-1), 3- (trimethoxysilyl) propyl acrylate was changed to acrylamide3- (trimethoxysilyl) propyl, and the amount of each monomer used was changed. Synthesized polyorganosylsesquioxane (SQ2-1) and (SQ2-3) in the same manner as in the synthesis of polyorganosylsesquioxane (SQ1-1).

In the synthesis of the polyorganosylsesquioxane (SQ2-1), the polyorgano was similar to the synthesis of the polyorganosylsesquioxane (SQ2-1) except that the polycondensation reaction time was changed to 2 hours. Silsesquioxane (SQ2-2) was synthesized.

(SQ3-1)
300 mmol (34.8 g) of 2-hydroxyethyl acrylate, 100 g of methyl isobutyl ketone, 300 mmol (61.5 g) of isocyanatopropyltrimethoxysilane, and 50 mg of Neostan U-600 were mixed and reacted at 60 ° C. for 5 hours. ..
Then, a mixture of 300 mmol (70.0 g) of acrylamide3- (trimethoxysilyl) propyl, 7.39 g of triethylamine, and 434 g of acetone was added to the above solution, and 73.9 g of pure water was further added using a dropping funnel. After dropping over 30 minutes, the mixture was heated to 50 ° C. and a polycondensation reaction was carried out for 10 hours.
Then, the reaction solution was cooled, neutralized with 12 mL of a 1N hydrochloric acid aqueous solution, 600 g of 1-methoxy-2-propanol was added, and then concentrated under the conditions of 30 mmHg and 50 ° C., 2-methoxy- with a solid content concentration of 30% by mass. A transparent liquid product, polyorganosylsesquioxane (SQ3-1), was obtained as a 1-propanol solution.

(SQ4-1)
In the synthesis of the polyorganosylsesquioxane (SQ3-1), the polyorganosylsesquioxane (SQ3) was changed from acrylamide3- (trimethoxysilyl) propyl to 3- (trimethoxysilyl) propyl acrylate. Polyorganosylsesquioxane (SQ4-1) was synthesized in the same manner as in the synthesis of -1).

(SQ5-1)
Acrylamide 2-hydroxyethyl 300 mmol (34.5 g), methyl isobutyl ketone 100 g, isocyanate 300 mmol (61.5 g), and Neostan U-600 50 mg were mixed and reacted at 60 ° C. for 5 hours.
Then, a mixture of 300 mmol (70.0 g) of acrylamide3- (trimethoxysilyl) propyl, 7.39 g of triethylamine, and 434 g of acetone was added to the above solution, and 73.9 g of pure water was further added using a dropping funnel. After dropping over 30 minutes, the mixture was heated to 50 ° C. and a polycondensation reaction was carried out for 10 hours.
Then, the reaction solution was cooled, neutralized with 12 mL of a 1N hydrochloric acid aqueous solution, 600 g of 1-methoxy-2-propanol was added, and then concentrated under the conditions of 30 mmHg and 50 ° C., 2-methoxy- with a solid content concentration of 30% by mass. A clear liquid product, polyorganosylsesquioxane (SQ5-1), was obtained as a 1-propanol solution.

(SQ6-1)
A mixture of 300 mmol (70.8 g) of 3-glycidylpropyltrimethoxysilane, 300 mmol (70.0 g) of acrylamide3- (trimethoxysilyl) propyl, 7.39 g of triethylamine, and 434 g of acetone was added to the above solution. Further, 73.9 g of pure water was added dropwise over 30 minutes using a dropping funnel, and then heated to 50 ° C., and a polycondensation reaction was carried out for 10 hours.
Then, 0.3 mmol (21.6 g) of acrylic acid and 50 g of p-toluenesulfonic acid were added, and the mixture was reacted at 60 ° C. for 10 hours.
Then, the reaction solution was cooled, neutralized with 12 mL of a 1N hydrochloric acid aqueous solution, 600 g of 1-methoxy-2-propanol was added, and then concentrated under the conditions of 30 mmHg and 50 ° C., 2-methoxy- with a solid content concentration of 30% by mass. A clear liquid product, polyorganosylsesquioxane (SQ6-1), was obtained as a 1-propanol solution.

(SQ7-1)
300 mmol (53.8 g) of 3-aminopropyltrimethoxysilane, 300 g of tetrahydrofuran, and 300 mmol (30.4 g) of triethylamine were mixed, and the solution was cooled to 5 ° C. or lower. 300 mmol (33.6 g) of chloroacetic acid chloride was added dropwise to the cooled solution, and the temperature was raised to room temperature after the reaction.
300 g of ethyl acetate and 300 g of water were added to the obtained solution, and the organic phase was concentrated after separation.
The obtained concentrate was mixed with 300 g of tetrahydrofuran, 300 mmol (21.6 g) of acrylic acid, and 300 mmol (30.4 g) of triethylamine, and reacted at 50 ° C. for 6 hours. Then, 600 g of ethyl acetate and 600 g of water were added, and after liquid separation, the organic phase was concentrated.
A mixture of 7.39 g of triethylamine and 434 g of acetone is added to the obtained concentrate, and 73.9 g of pure water is further added dropwise over 30 minutes using a dropping funnel, and then heated to 50 ° C. for polycondensation. The reaction was carried out for 10 hours. Then, the reaction solution is cooled, neutralized with 12 mL of a 1N hydrochloric acid aqueous solution, 600 g of 1-methoxy-2-propanol is added, and the mixture is concentrated under the conditions of 30 mmHg and 50 ° C. to 2-methoxy with a solid content concentration of 30% by mass. A transparent liquid product, polyorganosylsesquioxane (SQ7-1), was obtained as a -1-propanol solution.

(SQ8-1)
300 mmol (70.0 g) of acrylamide3- (trimethoxysilyl) propyl was added to the concentrate of (SQ7-1) before the polycondensation reaction, and then the solid content was subjected to the same polycondensation reaction as (SQ7-1). A clear liquid product, polyorganosylsesquioxane (SQ8-1), was obtained as a 2-methoxy-1-propanol solution having a concentration of 30% by mass.

(SQ-1x)
600 mmol (69.6 g) of 2-hydroxyethyl acrylate, 200 g of methyl isobutyl ketone, 600 mmol (123.0 g) of isocyanatopropyltrimethoxysilane, and 50 mg of Neostan U-600 were mixed and reacted at 60 ° C. for 5 hours. ..
Then, a mixture of 7.39 g of triethylamine and 434 g of acetone was added to the above solution, and 73.9 g of pure water was further added dropwise over 30 minutes using a dropping funnel, and then heated to 50 ° C. for a polycondensation reaction. Was carried out for 10 hours.
Then, the reaction solution was cooled, neutralized with 12 mL of a 1N hydrochloric acid aqueous solution, 600 g of 1-methoxy-2-propanol was added, and then concentrated under the conditions of 30 mmHg and 50 ° C., 2-methoxy- with a solid content concentration of 30% by mass. A clear liquid product, polyorganosylsesquioxane (SQ-1x), was obtained as a 1-propanol solution.

(SQ-2x)
600 mmol (107.6 g) of 3-aminopropyltrimethoxysilane and 332 g of methyl isobutyl ketone were mixed, and the solution was cooled to 5 ° C. or lower. 600 mmol (84.6 g) 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 7.39 g of triethylamine and 434 g of acetone was added to the above solution, and 73.9 g of pure water was further added dropwise over 30 minutes using a dropping funnel, and then heated to 50 ° C. for a polycondensation reaction. Was carried out for 10 hours.
Then, the reaction solution was cooled, neutralized with 12 mL of a 1N hydrochloric acid aqueous solution, 600 g of 1-methoxy-2-propanol was added, and then concentrated under the conditions of 30 mmHg and 50 ° C., 2-methoxy- with a solid content concentration of 30% by mass. A clear liquid product, polyorganosylsesquioxane (SQ-2x), was obtained as a 1-propanol solution.

(SQ-3x)
A mixture of 600 mmol (140.0 g) of acrylamide 3- (trimethoxysilyl) propyl, 7.39 g of triethylamine, and 434 g of acetone is added to the above solution, and 73.9 g of pure water is further added to 30 using a dropping funnel. After dropping over a minute, the mixture was heated to 50 ° C. and a polycondensation reaction was carried out for 10 hours.
Then, the reaction solution was cooled, neutralized with 12 mL of a 1N hydrochloric acid aqueous solution, 600 g of 1-methoxy-2-propanol was added, and then concentrated under the conditions of 30 mmHg and 50 ° C., 2-methoxy- with a solid content concentration of 30% by mass. A clear liquid product, polyorganosylsesquioxane (SQ-3x), was obtained as a 1-propanol solution.

(SQ-4x)
120 mmol (60 mL) of a methanol solution of 2 mol / L methylamine and 166 g of methyl isobutyl ketone were mixed, and the solution was cooled to 5 ° C. or lower. To the cooled solution, 120 mmol (16.9 g) of 2-acryloyloxyethyl isocyanate was added dropwise, and the temperature was raised to room temperature after the reaction.
Then, a mixture of 480 mmol (112.5 g) of 3- (trimethoxysilyl) propyl acrylate, 7.39 g of triethylamine, and 434 g of acetone was added to the above solution, and 73.9 g of pure water was further added using a dropping funnel. Then, the mixture was added dropwise over 30 minutes and then heated to 50 ° C., and a polycondensation reaction was carried out for 10 hours.
Then, the reaction solution was cooled, neutralized with 12 mL of a 1N hydrochloric acid aqueous solution, 600 g of 1-methoxy-2-propanol was added, and then concentrated under the conditions of 30 mmHg and 50 ° C., 2-methoxy- with a solid content concentration of 30% by mass. A clear liquid product, polyorganosylsesquioxane (SQ-4x), was obtained as a 1-propanol solution.

(SQ-5x)
A mixture of 600 mmol (141.6 g) of 3-glycidylpropyltrimethoxysilane, 7.39 g of triethylamine, and 434 g of acetone was added to the above solution, and 73.9 g of pure water was added over 30 minutes using a dropping funnel. After dropping the mixture, the mixture was heated to 50 ° C. and a polycondensation reaction was carried out for 10 hours.
Then, the reaction solution was cooled, neutralized with 12 mL of a 1N hydrochloric acid aqueous solution, 600 g of 1-methoxy-2-propanol was added, and then concentrated under the conditions of 30 mmHg and 50 ° C., 2-methoxy- with a solid content concentration of 30% by mass. A clear liquid product, polyorganosylsesquioxane (SQ-5x), was obtained as a 1-propanol solution.

The structure of each polymer used as polyorganosylsesquioxane (a1) is shown below. In the following structural formula, "SiO _1.5 " represents a silsesquioxane unit. The structural units of each polymer correspond to the structural units (A) and the structural units (B) in order from the structural units listed on the left side, and the composition ratio of each structural unit is indicated by a molar ratio.
Table 1 shows the hydrogen bond value, side chain length, number of side chain elements, and crosslinkable base value of each polymer calculated by the above method.

[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 the 2-methoxy-1-propanol solution containing the polyorganosylsesquioxane (SQ1-1). The content of each component was adjusted as follows, and the mixture was charged 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 a resin composition HC-1.

2-Methyl-1-propanol solution of polyorganosylsesquioxane (SQ1-1) (solid content concentration 30% by mass) 90.4 parts by mass Irgacure 127 (Irg.127) 5.0 parts by mass MIBK 4.6 parts by mass Department

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

(Manufacturing of hard coat film)
The above resin composition HC-1 was applied to a polyimide base material S-1 having a thickness of 30 μm using a wire bar # 18 so that the film thickness after curing was 18 μm, and a hard coat layer was applied onto the base material. A coating film was provided.
Next, after drying the hard coat layer coating film at 120 ° C. for 1 minute, the illuminance is 18 mW / cm ² and the irradiation amount is 160 mJ / cm using an air-cooled mercury lamp under the conditions of 25 ° C. and an oxygen concentration of 100 ppm (parts per million). The ultraviolet rays of ² were irradiated. In this way, the hard coat layer coating film was cured to obtain a laminate (hard coat film) of Example 1 having a hard coat layer on the base material.

[Examples 2 to 11, Comparative Examples 1 to 5]
The same as in Example 1 except that the polyorganosylsesquioxane (SQ1-1) used was changed to (SQ1-2) to (SQ8-1) and (SQ-1x) to (SQ-5x). , Examples 2 to 11 and Comparative Examples 1 to 5, respectively, were produced.

[Evaluation of hard coat film]
The produced hard coat films of Examples and Comparative Examples were evaluated by the following methods. The evaluation results are shown in Table 1.

(Pencil hardness)
The pencil hardness was evaluated according to JIS (JIS is Japanese Industrial Standards (Japanese Industrial Standards)) K5400. After adjusting the humidity of the hard coat films of each example and comparative example at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, the tests of H to 9H specified in JIS S 6006 were performed on five different surfaces of the hard coat layer. It was scratched with a pencil with a load of 4.9 N. After that, among the hardnesses of the pencils in which scratches were visually observed at 0 to 2 points, the pencil hardness having the highest hardness was used as the evaluation result. As for the pencil hardness, the higher the numerical value written before "H", the higher the hardness is preferable.

(Repeat bending resistance)
A sample film having a width of 15 mm and a length of 150 mm was cut out from the produced hard coat films of Examples and Comparative Examples, and allowed to stand at a temperature of 25 ° C. and a relative humidity of 65% for 1 hour or more. Then, a 180 ° folding resistance tester (IMC-0755 type, manufactured by Imoto Seisakusho Co., Ltd.) was used to repeatedly test the bending resistance with the base material inside. The testing machine used had the operation of bending the sample film along the curved surface of a rod (cylinder) with a diameter of 4 mm at a bending angle of 180 ° at the central part in the longitudinal direction, and then returning it to its original position (spreading the sample film). This test is repeated once.
When the above 180 ° bending test is repeated 300,000 times or more, A is defined as A, and B is defined as B when cracks occur 100,000 times or more and less than 300,000 times. Those with cracks were evaluated as C.
The presence or absence of cracks 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.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on May 17, 2019 (Japanese Patent Application No. 2019-93792), the contents of which are incorporated herein by reference.

Claims

A resin composition containing a polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The polyorganosylsesquioxane has a hydrogen bond value of 3.0 or more, a side chain length of 14 × 10-10 to 19 × 10-10 m, and a side chain length of 14 × 10-10 to 19 × 10-10 m.
The hydrogen bond value is represented by the following formula (1), and the side chain length represents the length from the Si atom to the end of the side chain, a resin composition.
Hydrogen bond value = number of hydrogen atoms that can form hydrogen bonds in one structural unit / molecular weight of one structural unit x 1000 ... (1)
A resin composition containing a polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The polyorganosylsesquioxane has a hydrogen bond value of 3.0 or more and a crosslinkable base value of 4.5 to 6.0.
The hydrogen bond value is represented by the following formula (1), and the crosslinkable base value is represented by the following formula (5).
Hydrogen bond value = number of hydrogen atoms that can form hydrogen bonds in one structural unit / molecular weight of one structural unit x 1000 ... (1)
Crosslinkable radix = number of crosslinkable groups in one structural unit / molecular weight of one structural unit x 1000 ... (5)
The polyorganosylsesquioxane has a hydrogen bond value of 3.0 or more, a side chain length of 14 × 10-10 to 19 × 10-10 m, and a crosslinkable base value of 4.5 to 6.0. The resin composition according to claim 1 or 2.
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. Stuff.
A structural unit (S1) in which the polyorganosylsesquioxane has a group containing a hydrogen atom capable of forming a hydrogen bond, and a structural unit (S2) having a crosslinkable group different from the structural unit (S1). The resin composition according to any one of claims 1 to 4, which contains and.
The resin composition according to claim 5, wherein the group containing a hydrogen atom capable of forming a hydrogen bond of the structural unit (S1) is at least one group selected from an amide group, a urethane group, and a urea group.
The resin composition according to claim 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.
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.
The resin composition according to any one of claims 1 to 8, wherein the polyorganosylsesquioxane has a weight average molecular weight of 10,000 to 1,000,000.
A hard coat film having a base material and a hard coat layer containing a cured product of the resin composition according to any one of claims 1 to 9.
The hard coat film according to claim 10, wherein the hard coat film has a pencil hardness of 3H or more, and cracks do not occur when the 180 ° bending test is repeated 100,000 times with a radius of curvature of 2 mm with the base material inside.
A polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The hydrogen bond value is 3.0 or more, the side chain length is 14 × 10 -10 to 19 × 10 -10 m, and the side chain length is 14 × 10 -10 to 19 × 10 -10 m.
The hydrogen bond value is represented by the following formula (1), and the side chain length is a polyorganosylsesquioxane, wherein the side chain length represents the length from a Si atom to the end of the side chain.
Hydrogen bond value = number of hydrogen atoms that can form hydrogen bonds in one structural unit / molecular weight of one structural unit x 1000 ... (1)
A polyorganosylsesquioxane having a group containing a hydrogen atom capable of forming a hydrogen bond.
The hydrogen bond value is 3.0 or more, the crosslinkable base value is 4.5 to 6.0, and
The hydrogen bond value is represented by the following formula (1), and the crosslinkable base value is a polyorganosylsesquioxane represented by the following formula (5).
Hydrogen bond value = number of hydrogen atoms that can form hydrogen bonds in one structural unit / molecular weight of one structural unit x 1000 ... (1)
Crosslinkable radix = number of crosslinkable groups in one structural unit / molecular weight of one structural unit x 1000 ... (5)
The 12th or 13th claim, wherein the hydrogen bond value is 3.0 or more, the side chain length is 14 × 10 -10 to 19 × 10 -10 m, and the crosslinkable base value is 4.5 to 6.0. Polyorganosylsesquioxane.