JP7064650B2 - Laminates, articles with laminates, and image display devices - Google Patents

Description

The present invention relates to a laminate, an article provided with the laminate, and an image display device.

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

For example, Patent Document 1 describes a hard coat film having a hard coat layer made of a cured product of a curable composition containing a cationically curable silicone resin and a leveling agent on a substrate.

Japanese Patent Laid-Open No. 2018-83915

In recent years, for example, in smartphones and the like, there has been an increasing need for ultra-thin and flexible displays, and along with this, it is possible to achieve both scratch resistance and repeated bending resistance (property that cracks do not occur even when repeatedly bent). There is a strong demand for optical films. Further, it is also required that there is little whitening due to uneven film thickness that occurs when the coating layer such as the hard coat layer is dried.
As a result of studies by the present inventors, it was found that the hard-coated film described in Patent Document 1 cannot achieve both scratch resistance and repeated bending resistance.
An object of the present invention is to provide a laminated body having excellent scratch resistance and repeated bending resistance and suppressed whitening, an article provided with the laminated body, and an image display device.

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

<1>
A laminate having a base material, a hard coat layer, and a scratch resistant layer in this order.
The above hard coat layer is
A composition for forming a hard coat layer containing a polyorganosylsesquioxane (a1) having a cationically polymerizable group, a group containing a fluorine atom, a cationically polymerizable group, and a polymer (S) having a radically polymerizable group. Including cured products
The scratch-resistant layer contains a cured product of a scratch-resistant layer-forming composition containing a radically polymerizable compound (c1).
When the 180 ° bending test was repeated 300,000 times with the scratch-resistant layer inside and a radius of curvature of 2 mm, no cracks occurred and cracks did not occur.
A laminate that does not cause scratches when the surface of the scratch-resistant layer is rubbed 100 times back and forth while applying a load of 1 kg / cm ² with # 0000 steel wool.
<2>
The laminate according to <1>, wherein the polymer (S) is polyorganosyl sesquioxane.
<3>
The polymer (S) is represented by the following general formula (S-1), the following general formula (S-2), and the following general formula (S-3). The laminate according to <2>, which has a structural unit.

In the general formula (S-1), L ₁ represents a single bond or a divalent linking group, and Q ₁ represents a group containing a fluorine atom.
In the general formula (S-2), L ₂ represents a single bond or a divalent linking group, and Q ₂ represents a cationically polymerizable group.
In the general formula (S-3), L ₃ represents a single bond or a divalent linking group, and Q ₃ represents a radically polymerizable group.
<4>
Item 3. The laminate described.
<5>
The item according to any one of <1> to <4>, wherein the molar ratio of the structural unit having a radically polymerizable group in the polymer (S) is more than 1 mol% with respect to all the structural units. Laminated body.
<6>
The laminate according to any one of <1> to <5>, wherein the scratch-resistant layer has a film thickness of less than 3.0 μm.
<7>
Item 6. The laminate according to any one of <1> to <6>, wherein the substrate contains at least one polymer selected from an imide-based polymer and an aramid-based polymer.
<8>
The laminate according to any one of <1> to <7>, wherein the cationically polymerizable group in the polyorganosylsesquioxane (a1) is an epoxy group.
<9>
The composition for forming a hard coat layer contains 0.001 to 5% by mass of the polymer (S) with respect to the total solid content of the composition for forming a hard coat layer, <1> to <8>. The laminate according to any one of the above items.
<10>
An article comprising the laminate according to any one of <1> to <9>.
<11>
An image display device provided with the laminate according to any one of <1> to <9> as a surface protective film.

According to the present invention, it is possible to provide a laminate having excellent scratch resistance and repeated bending resistance and suppressed whitening, an article provided with the laminate, and an image display device.

Hereinafter, embodiments for carrying out the present invention will be described in detail, but the present invention is not limited thereto. In addition, in this specification, when a numerical value represents a physical characteristic value, a characteristic value, 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" and the like.

[Laminate]
The laminate of the present invention is
A laminate having a base material, a hard coat layer, and a scratch resistant layer in this order.
The above hard coat layer is
A composition for forming a hard coat layer containing a polyorganosylsesquioxane (a1) having a cationically polymerizable group, a group containing a fluorine atom, a cationically polymerizable group, and a polymer (S) having a radically polymerizable group. Including cured products
The scratch-resistant layer contains a cured product of a scratch-resistant layer-forming composition containing a radically polymerizable compound (c1).
When the 180 ° bending test was repeated 300,000 times with the scratch-resistant layer inside and a radius of curvature of 2 mm, no cracks occurred and cracks did not occur.
It is a laminated body that does not cause scratches when the surface of the scratch-resistant layer is rubbed 100 times back and forth while applying a load of 1 kg / cm ² with # 0000 steel wool.

Although the details of the mechanism by which the laminate of the present invention is excellent in scratch resistance and repeated bending resistance are not clear, the present inventors speculate as follows.
Polyorganosylsesquioxane (a1) having a cationically polymerizable radical is a material capable of imparting hardness and bending resistance to the hard coat layer, but polyorganosylsesquioxane (a1) having a cationically polymerizable radical can be used. When a cured product of a scratch-resistant layer-forming composition containing a radically polymerizable compound (c1) is formed on a hard coat layer containing a cured product of the composition for forming a hard coat layer containing the radical-polymerizable layer, the hard coat layer is a cationic polymerization system. Since the scratch-resistant layer is a radical polymerization system, it is probable that the polymerization systems of the two layers are different, the adhesion between the layers is weak, and the improvement in scratch resistance is low.
In the present invention, the polymer (S) is obtained by adding a polymer (S) having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group to the composition for forming a hard coat layer. It is considered that the polymer functions as an interlayer adhesion agent, the adhesion between layers is strengthened, and the scratch resistance is excellent.
More specifically, since the polymer (S) has a group containing a fluorine atom, the polymer (S) is unevenly distributed on the surface of the hard coat layer (surface on the air interface side) when the composition for forming the hard coat layer is applied. Therefore, the layers can be efficiently adhered to each other. Further, it is considered that the action of the group containing a fluorine atom reduces the surface tension of the coating liquid and suppresses marangoni convection, uneven wind drying, and the like, so that whitening caused by surface scattering can be suppressed.
Since the polymer (S) has a cationically polymerizable group, it can be bonded to the polyorganosylsesquioxane (a1) having a cationically polymerizable group, which is a material of the hard coat layer, by a polymerization reaction.
Further, since the polymer (S) has a radically polymerizable group, it can be bonded to the radically polymerizable compound (c1) which is a material of the scratch resistant layer by a polymerization reaction.
Therefore, since the polymer (S) can be bonded to both the material of the hard coat layer and the material of the scratch resistant layer, the adhesion between the layers can be improved, and thereby the scratch resistance can be improved. it is conceivable that.

<Base material>
The laminate of the present invention contains a base material.
The substrate has a transmittance of 70% or more, more preferably 80% or more, and even more preferably 90% or more in the visible light region.

(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 break 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 substrate preferably contains at least one polymer selected from imide-based polymers and aramid-based polymers.

Further, the base material can also 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 brittle improving agent, 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 breaking and bending alone may be used alone as a base material for a film, or a softening material may be mixed alone, 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 substrate depending on the intended use. 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 may be added to the material preparation step by adding the step of adding and preparing the additive. 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.

The above additives may be used alone or in combination of two or more.

(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 Japanese Patent Application Laid-Open No. 2013-11835. In the present invention, an ultraviolet absorber having high heat resistance and low volatilization is preferable. Examples of such UV absorbers 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, the base material preferably 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 of the repeating structural units 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. In the formula (a'), G ³ represents a tetravalent organic group, and A ³ represents a divalent organic group. ^G4 and A4 in the formula (b) represent divalent organic groups, ^respectively .

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 substrate containing the imide-based 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 linked to each other directly or 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. As used herein, 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 are linked to each other directly or by a linking 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, etc., having 1 to 1 carbon atoms. 3 represents an alkyl group 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 further 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. Examples of the heteroatom include O, N or S.

Specific examples of G include the groups represented by the following formulas (20), formulas (21), formulas (22), formulas (23), formulas (24), formulas (25) or formulas (26). Will be. * In the formula indicates a bond. Z in the 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 are 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 binding 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 them (which may be the same) and are linked to each other directly or by a linking group. Examples of the hetero atom include O, N or S, and examples of the bonding group include -O-, an alkylene group having 1 to 10 carbon atoms, -SO _2- , -CO- or -CO-NR- (R is methyl). Examples thereof include an alkyl group having 1 to 3 carbon atoms such as a group, an ethyl group, and a propyl group, or a hydrogen atom).

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 a group represented by the following formula (30), formula (31), formula (32), formula (33) or formula (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 a fluorinated substituent.

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).

G3 in formula (a') can be selected from the same groups as G in formula ⁽ PI). A3 in formula (a') can be selected from the same groups as A in formula ⁽ PI).

G4 in the 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. As an example of G ⁴ , 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 is mentioned. Can be done. A4 in formula (b) can be selected from the same groups as A in formula ⁽ PI).

The imide-based polymer contained in the substrate 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 aromatic tetracarboxylic acid compounds, alicyclic tetracarboxylic acid compounds and acyclic aliphatic tetracarboxylic acid compounds. These may be used in combination of two or more. The tetracarboxylic acid compound is preferably a tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and acyclic aliphatic tetracarboxylic acid 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 substrate 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 and their related acid chloride compounds, 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 solubility of the imide-based polymer in a solvent and 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 substrate 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 acid, alicyclic dicarboxylic acid, acyclic aliphatic dicarboxylic acid and acid chloride compounds related thereto, acid anhydride 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 substrate containing the imide-based polymer, the dicarboxylic acid compound is an alicyclic dicarboxylic acid compound having a fluorine-based substituent or an aromatic dicarboxylic acid compound having a fluorine-based substituent. Is more preferable.

Examples of the 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-based polymer in the solvent and the transparency and flexibility when the substrate containing the imide-based polymer is formed, the diamines are selected from the alicyclic diamine and the aromatic diamine 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, 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 increase and the processability tends to decrease.

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 substrate 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-based polymer can be improved. The halogen atom is preferably a fluorine atom. The content of the halogen atom 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-based polymer include at least one compound selected from the group consisting of benzophenone-based compounds, salicylate-based compounds, benzotriazole-based compounds, and triazine-based compounds.
As used herein, the term "system compound" refers to a derivative of a compound to which the "system compound" is attached. For example, the "benzophenone-based compound" refers to a compound having benzophenone as a maternal skeleton and a substituent bonded to 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. Since 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-based 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-based polymer.

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

In the base material containing the imide-based polymer, the compounding 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 compounding 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-based polymer may further contain components other than the imide-based polymer and the inorganic material as long as the transparency and flexibility are not significantly impaired. Examples of the components other than the imide polymer and the inorganic material include colorants such as antioxidants, mold release agents, stabilizers and brewing agents, flame retardants, lubricants, thickeners and leveling agents. The ratio of the components other than the imide-based polymer and the inorganic material is preferably more than 0% and 20% by mass or less, more preferably more than 0% and 10% by mass or less with respect to the mass of the base material. ..

When the substrate 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. This atomic number ratio Si / N is determined by evaluating the composition of the substrate containing the 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 even 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 becomes thin, 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 even if the base material is bent a plurality of times, the base material does not break. 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 manufacturing the base material)
The base material 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 method (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 may be heated for drying and / or baking of the coating. 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 substrate 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.

At least one surface of the substrate may be surface treated.

<Hard coat layer>
The laminate of the present invention includes a hard coat layer.
The hardcourt layer is formed on at least one surface of the substrate.
The laminate of the present invention has at least one hardcoat layer between the substrate and the scratch resistant layer.
The hard coat layer of the laminate of the present invention is a polyorganosylsesquioxane (a1) having a cationically polymerizable group, and a polymer having a group containing a fluorine atom, a cationically polymerizable group and a radically polymerizable group (a 1). Contains a cured product of the composition for forming a hard coat layer containing S).

(Polyorganosylsesquioxane having a cationically polymerizable group (a1))
Polyorganosyl sesquioxane (a1) having a cationically polymerizable group (also referred to as “polyorganosyl sesquioxane (a1)”) will be described.
The cationically polymerizable group in the polyorganosylsesquioxane (a1) is not particularly limited, and a generally known cationically polymerizable group can be used. Specifically, an alicyclic ether group and a cyclic acetal are used. Examples thereof include a group, a cyclic lactone group, a cyclic thioether group, a spirorthoester group, a vinyloxy group and the like. As the cationically polymerizable group, an alicyclic ether group and a vinyloxy group are preferable, an epoxy group, an oxetanyl group and a vinyloxy group are particularly preferable, and an epoxy group is most 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).

The polyorganosylsesquioxane (a1) is preferably a polyorganosylsesquioxane represented by the following general formula (1).

In the general formula (1), Rb represents a group containing a cationically polymerizable group, and Rc represents a monovalent group. q and r represent the ratio of Rb and Rc in the general formula (1), q + r = 100, q is more than 0, and r is 0 or more. When there are a plurality of Rb and Rc in the general formula (1), the plurality of Rb and Rc may be the same or different. When there are a plurality of Rc in the general formula (1), the plurality of Rc may form a bond with each other.

[SiO _1.5 ] in the general formula (1) represents a structural portion composed of a siloxane bond (Si—O—Si) in the polyorganosyl sesquioxane.
Polyorganosilsesquioxane is a network-type polymer or polyhedron 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 by siloxane bonds. It can form cage structures and 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 ladder structure. By forming the ladder structure, the deformation recovery of the laminated body 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 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 (1), Rb represents a group containing a cationically polymerizable group, and preferably represents a group containing an epoxy group.
Examples of the group containing an epoxy group include known groups having an oxylan ring.
Rb is preferably a group represented by the following formulas (1b) to (4b).

In the above formulas (1b) to (4b), ** represents a connecting portion with Si in the general formula (1), and R ^1b , R ^2b , R ^3b and R ^4b are single-bonded or divalent linking groups. Represents.
R ^1b , R ^2b , R ^3b and R ^4b preferably represent substituted or unsubstituted alkylene groups.
As the alkylene group represented by R ^1b , R ^2b , R ^3b and R ^4b , a linear or branched alkylene group having 1 to 10 carbon atoms is preferable, and for example, a methylene group, a methylmethylene group, a dimethylmethylene group and an ethylene are preferable. Examples thereof include a group, an i-propylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-decylene group and the like.
When the alkylene group represented by R ^1b , R ^2b , R ^3b and R ^4b has a substituent, the substituent includes a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group and a cyano group. Groups, silyl groups and the like can be mentioned.
As R ^1b , R ^2b , R ^3b and R ^4b , an unsubstituted linear alkylene group having 1 to 4 carbon atoms, an unsubstituted linear branched alkylene group having 3 or 4 carbon atoms is preferable, and an ethylene group is preferable. , N-propylene group or i-propylene group is more preferable, and ethylene group or n-propylene group is more preferable.

The polyorganosylsesquioxane (a1) preferably has an alicyclic epoxy group (a group having a condensed ring structure of an epoxy group and an alicyclic group). The Rb in the general formula (1) is preferably a group having an alicyclic epoxy group, more preferably a group having an epoxycyclohexyl group, and is a group represented by the above formula (1b). Is even more preferable.

In addition, Rb in the general formula (1) is a group bonded to a silicon atom (a group other than an alkoxy group and a halogen atom; for example, a group described later) in a hydrolyzable trifunctional silane compound used as a raw material of polyorganosylsesquioxane. It is derived from Rb etc. in the hydrolyzable silane compound represented by the formula (B) of.

Specific examples of Rb are shown below, but the present invention is not limited thereto. In the following specific example, ** represents a connecting portion with Si in the general formula (1).

In the general formula (1), Rc represents a monovalent group.
The monovalent group represented by Rc includes a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. Substituted aralkyl groups can be mentioned.

Examples of the alkyl group represented by Rc include an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, an s-butyl group, and a t-butyl group. Examples thereof include a linear or branched alkyl group such as a group and an isopentyl group.
Examples of the cycloalkyl group represented by Rc include a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the alkenyl group represented by Rc include an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a linear or branched alkenyl group such as a vinyl group, an allyl group and an isopropenyl group.
Examples of the aryl group represented by Rc include an aryl group having 6 to 15 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
Examples of the aralkyl group represented by Rc include an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

The above-mentioned substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted aryl group, and substituted aralkyl group include hydrogen atoms or main ribs in each of the above-mentioned alkyl group, cycloalkyl group, alkenyl group, aryl group and aralkyl group. At least one selected from the group consisting of an ether group, an ester group, a carbonyl group, a halogen atom (fluorine atom, etc.), an acrylic group, a methacryl group, a mercapto group, and a hydroxy group (hydroxyl group) in part or all of the case. Examples thereof include groups substituted with.

Rc is preferably a substituted or unsubstituted alkyl group, and more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms.

When there are a plurality of Rc in the general formula (1), the plurality of Rc may form a bond with each other. It is preferable that two or three Rc form a bond with each other, and more preferably two Rc form a bond with each other.

The group (Rc ₂ ) formed by bonding two Rc to each other is preferably an alkylene group formed by bonding a substituted or unsubstituted alkyl group represented by the above-mentioned Rc.

Examples of the alkylene group represented by Rc ₂ include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an s-butylene group, a t-butylene group, an n-pentylene group and an isopentylene group. s-pentylene group, t-pentylene group, n-hexylene group, isohexylene group, s-hexylene group, t-hexylene group, n-heptylene group, isoheptylene group, s-heptylene group, t-heptylene group, n-octylene group. , Isooctylene group, s-octylene group, t-octylene group and other linear or branched alkylene groups.

As the alkylene group represented by Rc ₂ , an unsubstituted alkylene group having 2 to 20 carbon atoms is preferable, an unsubstituted alkylene group having 2 to 20 carbon atoms is more preferable, and an unsubstituted alkylene group having 2 to 8 carbon atoms is more preferable. It is an alkylene group, and particularly preferably an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group and an n-octylene group.

The group (Rc ₃ ) formed by bonding three Rc to each other is preferably a trivalent group in which any hydrogen atom in the alkylene group is reduced by one in the above-mentioned alkylene group represented by Rc ₂ . ..

In addition, Rc in the general formula (1) is a group bonded to a silicon atom (a group other than an alkoxy group and a halogen atom; for example, the formula described later) in a hydrolyzable silane compound used as a raw material of polyorganosylsesquioxane. It is derived from _Rc1 to Rc3 _, etc. in the hydrolyzable silane compounds represented by (C1) to (C3).

In the general formula (1), q is more than 0 and r is 0 or more.
q / (q + r) is preferably 0.5 to 1.0. By making the number of groups represented by Rb more than half of the total amount of groups represented by Rb or Rc contained in polyorganosylsesquioxane (a1), a network formed by organic cross-linking groups is sufficiently formed. Therefore, the hardness and the performance of repeated bending resistance can be kept good.
q / (q + r) is more preferably 0.7 to 1.0, further preferably 0.9 to 1.0, and particularly preferably 0.95 to 1.0.

In the general formula (1), it is also preferable that there are a plurality of Rc and the plurality of Rc form a bond with each other. In this case, r / (q + r) is preferably 0.005 to 0.20.
r / (q + r) is more preferably 0.005 to 0.10, further preferably 0.005 to 0.05, and particularly preferably 0.005 to 0.025.

The number average molecular weight (Mn) of polyorganosilsesquioxane (a1) in terms of standard polystyrene by gel permeation chromatography (GPC) is preferably 500 to 6000, more preferably 1000 to 4500, and even more preferably. It is 1500 to 3000.

The molecular weight dispersion (Mw / Mn) of polyorganosilsesquioxane (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: Tetrahydrofuran (THF), 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 polyorganosyl sesquioxane (a1)>
The polyorganosylsesquioxane (a1) can be produced by a known production method, and is not particularly limited, and can be produced by a method of hydrolyzing and condensing one or more hydrolyzable silane compounds. As the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (a compound represented by the following formula (B)) for forming a siloxane structural unit containing an epoxy group is used as the hydrolyzable silane compound. Is preferable.
When r in the general formula (1) is more than 0, it is preferable to use a compound represented by the following formula (C1), (C2) or (C3) in combination as the hydrolyzable silane compound.

Rb in the formula (B) has the same meaning as Rb in the general formula (1), and the same applies to preferred examples.

X ² in the formula (B) represents an alkoxy group or a halogen atom.
Examples of the alkoxy group in X ² 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 in X ² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
As X ² , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. The three ^X2s may be the same or different.

The compound represented by the above formula (B) is a compound that forms a siloxane constituent unit having Rb.

Rc ₁ in the formula (C1) has the same meaning as Rc in the general formula (1), and the same applies to preferred examples.
Rc ₂ in the formula (C2) has the same meaning as the group (Rc ₂ ) formed by binding two Rc in the general formula (1) to each other, and the same applies to preferred examples.
Rc ₃ in the formula (C3) has the same meaning as the group (Rc ₃ ) formed by binding the three Rc in the general formula (1) to each other, and the same applies to preferred examples.

X ³ in the above formulas (C1) to (C3) has the same meaning as X ² in the above formula (B), and the same applies to preferred examples. The plurality of ^X3s may be the same or different from each other.

As the hydrolyzable silane compound, a hydrolyzable silane compound other than the compounds represented by the above formulas (B) and (C1) to (C3) may be used in combination. Examples thereof include hydrolyzable trifunctional silane compounds, hydrolyzable monofunctional silane compounds, and hydrolyzable bifunctional silane compounds other than the compounds represented by the above formulas (B) and (C1) to (C3).

When Rc is derived from Rc ₁ to Rc ₃ in the hydrolyzable silane compounds represented by the above formulas (C1) to (C3), in order to adjust q / (q + r) in the general formula (1), the above The compounding ratio (molar ratio) of the compounds represented by the formulas (B) and (C1) to (C3) may be adjusted.
Specifically, for example, in order to set q / (q + r) to 0.5 to 1.0, the value represented by the following (Z2) is set to 0.5 to 1.0, and these compounds are hydrolyzed. And it may be produced by a method of condensing.
(Z2) = compound represented by the formula (B) (molar amount) / {compound represented by the formula (B) (molar amount) + compound represented by the formula (C1) (molar amount) + formula (C2) ) × 2 + compound (molar amount) represented by the formula (C3) × 3}

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. It should be noted that one type of solvent 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 can be appropriately adjusted 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. ..

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 alkaline catalyst.
Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid and p. -Sulphonic acid such as toluene sulfonic acid; solid acid such as active clay; Lewis acid such as iron chloride can be mentioned.
Examples of the alkaline catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide. Hydroxide; Alkaline metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; Alkaline earth metal carbonate such as magnesium carbonate; Lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate Hydrogen carbonates of alkali metals such as; organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate, cesium acetate (eg, acetates); organic acid salts of alkaline earth metals such as magnesium acetate (eg, acetates). Acetate); 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; triethylamine, N-methyl Alkali such as piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5-ene (tertiary amine, etc.); pyridine , 2,2'-Bipylidyl, 1,10-Phenantrolin and other nitrogen-containing aromatic heterocyclic compounds and the like.
It should be noted that one type of catalyst may be used alone, or two or more types may be used in combination. Further, the catalyst can also be used in a state of being dissolved or dispersed in water, an organic solvent or the like.
The catalyst is preferably a base catalyst. By using a base catalyst, the condensation rate of polyorganosyl sesquioxane can be increased, and the deformation recovery rate at the time of curing can be kept good.

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 hydrolysis and condensation reactions is not particularly limited, and can be appropriately adjusted within the range of 0.5 to 20 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound.

The method for adding 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.

As the reaction conditions for hydrolyzing and condensing the hydrolyzable silane compound, it is particularly possible to select reaction conditions such that the condensation rate of polyorganosylsesquioxane (a1) is 80% or more. is important. The reaction temperature of the hydrolysis and condensation reaction is, for example, 40 to 100 ° C, preferably 45 to 80 ° C. By controlling the reaction temperature within the above range, the condensation rate tends to be controlled to 80% or more. The reaction time of the hydrolysis and condensation reaction is, for example, 0.1 to 10 hours, preferably 1.5 to 8 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, any of an inert gas atmosphere such as a nitrogen atmosphere and an argon atmosphere, and an oxygen presence such as under air, but the inert gas. The atmosphere is preferable.

Polyorganosyl sesquioxane (a1) can be obtained by the hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reactions, it is preferable to neutralize the catalyst in order to suppress ring opening of the epoxy group. Further, the polyorganosylsesquioxane (a1) was separated by, for example, water washing, pickling, 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.

In the hard coat layer, the condensation rate of polyorganosyl sesquioxane (a1) is preferably 80% or more from the viewpoint of film hardness. The condensation rate is more preferably 90% or more, further preferably 95% or more.
The condensation rate can be calculated by performing ²⁹ Si NMR (nuclear magnetic resonance) spectral measurement on a sample having a hard coat layer containing a cured product of polyorganosylsesquioxane (a1) and using the measurement results. Is.

In the cured product of polyorganosylsesquioxane (a1) having an epoxy group, it is preferable that the epoxy group is ring-opened by a polymerization reaction.
In the hard coat layer, the ring opening rate of the epoxy group of the cured product of the polyorganosylsesquioxane (a1) having an epoxy group is preferably 40% or more from the viewpoint of the hardness of the film. The ring-opening rate is more preferably 50% or more, further preferably 60% or more.
The ring opening rate is the FT-IR (Fourier Transform Infrared Spectroscopy) single reflection ATR (Attenuated Total) sample before and after the composition for forming a hard coat layer containing polyorganosylsesquioxane (a1) is completely cured and heat-treated. Reflection) measurement can be performed and calculated from the change in peak height derived from the epoxy group.

Only one type of polyorganosylsesquioxane (a1) may be used, or two or more types having different structures may be used in combination.

The content of polyorganosyl sesquioxane (a1) in the composition for forming a hard coat layer is preferably 50% by mass or more, preferably 70% by mass, based on the total solid content of the composition for forming a hard coat layer. The above is more preferable, and 80% by mass or more is further preferable. The upper limit of the content of polyorganosyl sesquioxane (a1) in the composition for forming a hard coat layer is preferably 99.9% by mass or less with respect to the total solid content of the composition for forming a hard coat layer. , 98% by mass or less, more preferably 97% by mass or less.
The total solid content is all components other than the solvent.

(Polymer (S) having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group)
A polymer (S) having a group containing a fluorine atom, a cationically polymerizable group, and a radically polymerizable group (also referred to as “polymer (S)”) will be described.
As described above, the polymer (S) can function as an interlayer adhesion agent that enhances the adhesion between the hard coat layer and the scratch resistant layer.

[Group containing fluorine atom]
The fluorine atom-containing group (also referred to as "fluorine-containing group") in the polymer (S) is a group containing at least one fluorine atom, and is, for example, a fluorine atom or an organic having at least one fluorine atom. Fluorine and the like can be mentioned. Examples of the organic group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, and a group formed by combining at least two of these, which are alkyl groups. Is preferable. Further, the above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group and aryl group may further have a substituent other than the fluorine atom.
The fluorine-containing group is preferably a fluoroalkyl group having 1 to 20 carbon atoms, more preferably a fluoroalkyl group having 2 to 15 carbon atoms, and further preferably a fluoroalkyl group having 4 to 10 carbon atoms. It is preferably a fluoroalkyl group having 4 to 8 carbon atoms, and is particularly preferable.
The number of fluorine atoms in one fluorine-containing group is preferably 3 or more, more preferably 5 or more, and even more preferably 9 or more.
The number of fluorine atoms in one fluorine-containing group is preferably 17 or less, and more preferably 13 or less.

The fluorine-containing group is preferably a group represented by the following general formula (f-1).

In the general formula (f-1), q1 represents an integer of 0 to 12, q2 represents an integer of 1 to 8, and Rq ₁ represents a hydrogen atom or a fluorine atom. * Represents the bond position.
q1 preferably represents an integer of 1 to 7, more preferably an integer of 1 to 5, and even more preferably 1 or 2.
q2 preferably represents an integer of 2 to 8, more preferably an integer of 4 to 8, and even more preferably an integer of 4 to 6.
Rq ₁ preferably represents a fluorine atom.

[Cation-polymerizable group]
The cationically polymerizable group in the polymer (S) is not particularly limited, and a generally known cationically polymerizable group can be used, specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, and the like. Examples thereof include a cyclic thioether group, a spiroorthoester group, and a vinyloxy group. As the cationically polymerizable group, an alicyclic ether group and a vinyloxy group are preferable, an epoxy group, an oxetanyl group and a vinyloxy group are particularly preferable, and an epoxy group is most 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 cationically polymerizable group may be a group represented by the following formula (e-1), a group represented by the following general formula (e-2), or a group represented by the following general formula (e-3). preferable.

In the general formula (e-2), R ^1a represents a hydrogen atom or a substituted or unsubstituted alkyl group.
In the general formula (e-3), R ^2a represents a substituted or unsubstituted alkyl group. q3 represents an integer of 0 to 2. When a plurality of R ^2a exist, they may be the same or different from each other.
In the formula (e-1), the general formula (e-2), and the general formula (e-3), * represents the bonding position.

In the general formula (e-2), R ^1a represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R ^1a preferably represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-hexyl group and the like.
Examples of the substituent when the alkyl group has a substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group and a silyl group.
R ^1a is preferably an unsubstituted linear alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.

In the general formula (e-3), R ^2a represents a substituted or unsubstituted alkyl group.
R ^2a preferably represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-hexyl group and the like.
Examples of the substituent when the alkyl group has a substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group and a silyl group.
R ^2a is preferably an unsubstituted linear alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
q3 represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[Radical polymerizable group]
The radically polymerizable group in the polymer (S) 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, an allyl group and the like, and a (meth) acryloyl group is preferable. In addition, each group mentioned above may have a substituent.

The molar ratio of the constituent units having a fluorine atom in the polymer (S) is preferably more than 1 mol% and less than 70 mol%, and more than 1 mol% and less than 50 mol% with respect to all the constituent units. More preferably, it is more preferably 3 mol% or more and 30 mol% or less, particularly preferably 5 mol% or more and 20 mol% or less, and most preferably 5 mol% or more and 10 mol% or less. When the molar content ratio of the structural unit having a fluorine atom in the polymer (S) is more than 1 mol% and less than 50 mol% with respect to all the structural units, the radical polymerizable group in the polymer (S) and the radical polymerizable group can be obtained. The polymerization reaction of the radically polymerizable compound (c1) contained in the scratch-resistant layer forming composition with the radically polymerizable group is less likely to be inhibited, the adhesion between the hard coat layer and the scratch-resistant layer is improved, and the scratch resistance is improved. It is preferable because it is easy to improve.

From the viewpoint of scratch resistance, the molar ratio of the constituent units having a cationically polymerizable group in the polymer (S) is preferably more than 25 mol% and 85 mol% or less, preferably 30 mol, with respect to all the constituent units. It is more preferably% or more and 85 mol% or less, and further preferably 30 mol% or more and 60 mol% or less.

From the viewpoint of scratch resistance, the molar ratio of the structural unit having a radically polymerizable group in the polymer (S) is preferably more than 1 mol% with respect to all the structural units, and is preferably 10 mol% or more and 90 mol. % Or less, more preferably 30 mol% or more and 60 mol% or less.

The weight average molecular weight (Mw) of the polymer (S) is preferably 500 to 50,000, more preferably 1000 to 30,000, still more preferably 1500 to 12000, even more preferably 1500 to 10000, and in particular. It is preferably 1500 to 6000, and most preferably 1500 to 4500.

The molecular weight dispersion (Mw / Mn) of the polymer (S) is, for example, 1.00 to 4.00, preferably 1.10 to 3.70, and more preferably 1.20 to 3.00. , More preferably 1.20 to 2.50. Mw represents the weight average molecular weight, and Mn represents the number average molecular weight.

Unless otherwise specified, the weight average molecular weight and the molecular weight dispersion of the polymer (S) are measured values (in terms of polystyrene) of GPC. For the weight average molecular weight, specifically, HLC-8220 (manufactured by Tosoh Corporation) was prepared as an apparatus, tetrahydrofuran was used as an eluent, TSKgel (registered trademark) G3000HXL + TSKgel (registered trademark) G2000HXL was used as a column, and the temperature was 23 ° C. , Measured using a differential refractive index (RI) detector under the condition of a flow rate of 1 mL / min.

Only one kind of polymer (S) may be used, or two or more kinds having different structures may be used in combination.

The content of the polymer (S) in the composition for forming a hard coat layer in the present invention is 0.001 to 0 with respect to the total solid content of the composition for forming a hard coat layer from the viewpoint of scratch resistance and suppression of whitening. It is preferably 5% by mass, more preferably 0.01 to 3% by mass, further preferably 0.1 to 2% by mass, and particularly preferably 0.1 to 1% by mass. ..

The structure of the polymer (S) is not particularly limited, but it is preferably polyorganosylsesquioxane or a (meth) acrylic polymer, and more preferably polyorganosylsesquioxane. When the polymer (S) is polyorganosyl sesquioxane, whitening is particularly reduced in the laminate of the present invention, which is preferable. Although the details of the reason for this are not clear, the composition for forming a hard coat layer in the present invention contains the above-mentioned polyorganosylsesquioxane (a1), so that the polymer (S) is a polyorganosylsesquioxane. This is considered to be because the compatibility with the polyorganosyl sesquioxane (a1) is high, and the uniformity is high near the surface of the hard coat layer (it does not become like microphase separation).

[Polyorganosyl sesquioxane (SS)]
When the polymer (S) is polyorganosylsesquioxane, the polymer (S) is also referred to as polyorganosylsesquioxane (SS).
The structure of polyorganosylsesquioxane (SS) is not particularly limited, and can have a structure that can be obtained as polyorganosylsesquioxane, and has, for example, a random structure, a ladder structure, a cage structure, and the like. Is preferable.
Polyorganosilsesquioxane (SS) is a silsesquioxane unit having a group containing a fluorine atom, a silsesquioxane unit having a cationically polymerizable group, and a silsesquioxane unit having a radically polymerizable group. It is preferable to have.

Polyorganosyl sesquioxane (SS) is a structural unit represented by the following general formula (S-1), a structural unit represented by the following general formula (S-2), and the following general formula (S-3). It is preferable to have a structural unit represented by.

In the general formula (S-1), L ₁ represents a single bond or a divalent linking group, and Q ₁ represents a group containing a fluorine atom.
In the general formula (S-2), L ₂ represents a single bond or a divalent linking group, and Q ₂ represents a cationically polymerizable group.
In the general formula (S-3), L ₃ represents a single bond or a divalent linking group, and Q ₃ represents a radically polymerizable group.

In the general formulas (S-1) to (S-3), "SiO _1.5 " represents a sesquioxane unit.

In polyorganosylsesquioxane (SS), the molar ratio of the constituent units represented by the general formula (S-1) is preferably more than 1 mol% and 70 mol% or less with respect to all the constituent units. It is more preferably 3 mol% or more and 50 mol% or less, and further preferably 5 mol% or more and 20 mol% or less.

In polyorganosylsesquioxane (SS), the molar ratio of the constituent units represented by the general formula (S-2) is preferably 15% 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, further preferably 30 mol% or more and 70 mol% or less, and particularly preferably 30 mol% or more and 60 mol% or less.

In polyorganosylsesquioxane (SS), the molar content ratio of the structural unit represented by the general formula (S-3) is preferably more than 1 mol% with respect to all the structural units, and is 10 mol%. It is more preferably 85 mol% or more, more preferably 15 mol% or more and 70 mol% or less, and further preferably 30 mol% or more and 60 mol% or less.

In the general formula (S-1), L ₁ represents a single bond or a divalent linking group. When L ₁ represents a divalent linking group, -O-, -CO-, -COO-, -OCO-, -S-, -SO _2- , -NR-, an organic linking group having 1 to 20 carbon atoms. (For example, an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, an arylene group which may have a substituent, etc.), or a linking group formed by combining two or more of these. And so on. The above R represents a hydrogen atom or a substituent.
In the general formula (S-1), Q ₁ represents a group containing a fluorine atom. The group containing a fluorine atom is the same as that described above.

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

In the general formula (S-1-f), q1 represents an integer of 0 to 12, q2 represents an integer of 1 to 8, and Rq ₁ represents a hydrogen atom or a fluorine atom.
The q1, q2, and Rq 1 in the general formula (S-1-f) are the same as the q1, q2, and Rq ₁ in the general formula (f- ₁ ) described above, respectively.

In the general formula (S-1-f), "SiO _1.5 " represents a sesquioxane unit.

In the general formula (S-2), L ₂ represents a single bond or a divalent linking group. A specific example when L ₂ represents a divalent linking group is the same as that of L ₁ , and an alkylene group having 1 to 10 carbon atoms which may have a substituent, —O—, —CO—, —COO− , -OCO-, -S-, or a linking group composed of two or more of these, and an alkylene group having 1 to 5 carbon atoms which may have a substituent, -O-, -CO- , -COO-, -OCO-, or a linking group formed by combining two or more of these is more preferable, and it has an alkylene group having 1 to 5 carbon atoms or a substituent which may have a substituent. It is more preferable that the linking group is a combination of an alkylene group having 1 to 5 carbon atoms and —O—.
In the general formula (S- ₂ ), Q2 represents a cationically polymerizable group. The cationically polymerizable group is the same as that described above.

The structural unit represented by the general formula (S-2) is a structural unit represented by the following general formula (S-2-e1), a structural unit represented by the following general formula (S-2-e2), or It is preferably a structural unit represented by the following general formula (S-2-e3).

In the general formula (S-2-e1), L ₂ represents a single bond or a divalent linking group.
In the general formula (S-2-e2), R ^1a represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ₂ represents a single bond or a divalent linking group.
In the general formula (S-2-e3), R ^2a represents a substituted or unsubstituted alkyl group. q3 represents an integer of 0 to 2. When a plurality of R ^2a exist, they may be the same or different from each other. L ₂ represents a single bond or a divalent linking group.

In the general formulas (S-2-e1), (S-2-e2), and (S-2-e3), "SiO _1.5 " represents a silsesquioxane unit.

L ₂ in the general formula (S-2-e1), (S-2-e2), and (S-2-e3) is the same as L ₂ in the above-mentioned general formula (S-2).
R ^1a in the general formula (S-2-e2) is the same as R ^1a in the above-mentioned general formula (e-2).
R ^2a and q3 in the general formula (S-2-e3) are the same as R ^2a and q3 in the above-mentioned general formula (e-3), respectively.

In the general formula (S-3), L ₃ represents a single bond or a divalent linking group. Specific examples and preferable ranges when L ₃ represents a divalent linking group are the same as those of L ₂ described above.
In the general formula (S- ₃ ), Q3 represents a radically polymerizable group. The radically polymerizable group is the same as that described above.

The structural unit represented by the general formula (S-3) is a structural unit represented by the following general formula (S-3-r1) or a structural unit represented by the following general formula (S-3-r2). It is preferable to have.

In the general formula (S-3-r1), L ₃ represents a single bond or a divalent linking group, and R ^3a represents a hydrogen atom or a methyl group.
In the general formula (S-3-r2), L ₃ represents a single bond or a divalent linking group.

In the general formulas (S-3-r1) and (S-3-r2), "SiO _1.5 " represents a sesquioxane unit.

L ₃ in the general formula (S-3-r1) and (S-3-r2) is the same as L ₃ in the above-mentioned general formula (S-3).

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

<Manufacturing method of polyorganosyl sesquioxane (SS)>
The method for producing polyorganosylsesquioxane (SS) is not particularly limited and 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 fluorine atom (preferably a compound represented by the following general formula (Sd-1)) and hydrolysis having a cationically polymerizable group. A sex trifunctional silane compound (preferably a compound represented by the following general formula (Sd-2)) and a hydrolyzable trifunctional silane compound having a radically polymerizable group (preferably represented by the following general formula (Sd-3)). It is preferable to use a compound).
The compound represented by the following general formula (Sd-1) corresponds to the structural unit represented by the above general formula (S-1), and the compound represented by the following general formula (Sd-2) corresponds to the above general formula (Sd-2). The compound represented by the following general formula (Sd-3) corresponds to the structural unit represented by the above general formula (S-3).

In the general formula (Sd- ¹ ), ^X4 to X6 independently represent an alkoxy group or a halogen atom, L ₁ represents a single bond or a divalent linking group, and Q ₁ represents a group containing a fluorine atom. show.
In the general formula (Sd-2), X ⁷ to X ⁹ independently represent an alkoxy group or a halogen atom, L ₂ represents a single bond or a divalent linking group, and Q ₂ represents a cationically polymerizable group.
In the general formula (Sd-3), X ¹⁰ to X ¹² independently represent an alkoxy group or a halogen atom, L ₃ represents a single bond or a divalent linking group, and Q ₃ represents a radically polymerizable group.

L ₁ and Q ₁ in the general formula (Sd-1) have the same meaning as L ₁ and Q ₁ in the general formula (S-1), respectively, and the preferable range is also the same.
L ₂ and Q ₂ in the general formula (Sd-2) have the same meaning as L ₂ and Q ₂ in the general formula (S-2), respectively, and the preferable range is also the same.
L ₃ and Q ₃ in the general formula (Sd-3) have the same meaning as L ₃ and Q ₃ in the general formula (S-3), respectively, and the preferable range is also the same.

^In the general formulas (Sd-1) to (Sd- ³ ), X4 to X12 each independently represent an alkoxy group or a halogen atom.
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 ⁴ to X ¹² , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. Note that X ⁴ to X ¹² may be the same or different from each other.

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

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. It should be noted that one type of solvent 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 alkaline catalyst.
The acid catalyst is not particularly limited, and is not particularly limited, 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. Alkaline earth metal hydroxides; Alkaline metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; Alkaline earth metal carbonates such as magnesium carbonate; Lithium hydrogen carbonate, sodium hydrogen carbonate, hydrogen carbonate Alkaline 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 Alkaline acid salts (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.
It should be noted that one type of catalyst may be used alone, or two or more types may be used in combination. Further, 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 hydrolysis and condensation reactions 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. can.

The method for adding 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 reaction 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, any of an inert gas atmosphere such as a nitrogen atmosphere and an argon atmosphere, and an oxygen presence such as under air, but the inert gas. The atmosphere is preferable.

Polyorganosyl sesquioxane (SS) 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, polyorganosylsesquioxane (SS) was used as a separation means such as water washing, pickling, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and a combination thereof. It may be separated and purified by a separation means or the like.

[(Meta) Acrylic Polymer (SA)]
When the polymer (S) is an acrylic polymer, the polymer (S) is also referred to as a (meth) acrylic polymer (SA).
The (meth) acrylic polymer (SA) preferably has a group containing a fluorine atom in the side chain and does not have a fluorine atom in the main chain from the viewpoint of adhesion to the scratch resistant layer. ..
The (meth) acrylic polymer (SA) has a structural unit represented by the following general formula (P-1), a structural unit represented by the following general formula (P-2), and the following general formula (P-3). It is preferable to have a structural unit represented by.

In the general formula (P-1), M ₁ represents a hydrogen atom or a methyl group, L ₄ represents a single bond or a divalent linking group, and Q ₄ represents a group containing a fluorine atom.
In the general formula (P-2), M ₂ represents a hydrogen atom or a methyl group, L ₅ represents a single bond or a divalent linking group, and Q ₅ represents a cationically polymerizable group.
In the general formula (P-3), M ₃ represents a hydrogen atom or a methyl group, L ₆ represents a single bond or a divalent linking group, and Q ₆ represents a radically polymerizable group.

In the general formula (P-1), L ₄ represents a single bond or a divalent linking group, and a specific example in the case where L ₄ represents a divalent linking group is described in the above-mentioned general formula (S-1). It is the same as _L1 .
In the general formula (P-1), _Q4 represents a group containing a fluorine atom. The group containing a fluorine atom is the same as that described above.

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

In the general formula (P-1-f), M ₁ represents a hydrogen atom or a methyl group, q1 represents an integer of 0 to 12, q2 represents an integer of 1 to 8, and Rq ₁ represents a hydrogen atom or a fluorine atom. Represents.
The q1, q2, and Rq ₁ in the general formula (P-1-f) are the same as q1, q2, and Rq ₁ in the above-mentioned general formula (f-1), respectively.

In the general formula (P-2), L ₅ represents a single bond or a divalent linking group. Specific examples and preferable ranges when L ₅ represents a divalent linking group are the same as those of L ₂ in the above-mentioned general formula (S-2).
In the general formula (P- ₂ ), Q2 represents a cationically polymerizable group. The cationically polymerizable group is the same as that described above.

The structural unit represented by the general formula (P-2) is a structural unit represented by the following general formula (P-2-e1), a structural unit represented by the following general formula (P-2-e2), or It is preferably a structural unit represented by the following general formula (P-2-e3).

In the general formula (P-2-e1), M ₂ represents a hydrogen atom or a methyl group, and L ₅ represents a single bond or a divalent linking group.
In the general formula (P-2-e2), M ₂ represents a hydrogen atom or a methyl group, R ^1a represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ₅ represents a single bond or a divalent linking group. show.
In the general formula (P-2-e3), M ₂ represents a hydrogen atom or a methyl group, and R ^2a represents a substituted or unsubstituted alkyl group. q3 represents an integer of 0 to 2. When a plurality of R ^2a exist, they may be the same or different from each other. L ₅ represents a single bond or a divalent linking group.

L ₅ in the general formula (P-2-e1), (P-2-e2), and (P-2-e3) is the same as L ₅ in the above-mentioned general formula (P-2).
R ^1a in the general formula (P-2-e2) is the same as R ^1a in the above-mentioned general formula (e-2).
R ^2a and q3 in the general formula (P-2-e3) are the same as R ^2a and q3 in the above-mentioned general formula (e-3), respectively.

In the general formula (P-3), L ₆ represents a single bond or a divalent linking group. Specific examples and preferable ranges when L ₆ represents a divalent linking group are the same as those of L ₃ in the above-mentioned general formula (S-3).
In the general formula (P _- 3), Q6 represents a radically polymerizable group. The radically polymerizable group is the same as that described above.

The structural unit represented by the general formula (P-3) is a structural unit represented by the following general formula (P-3-r1) or a structural unit represented by the following general formula (P-3-r2). It is preferable to have.

In the general formula (P-3-r1), M ₃ represents a hydrogen atom or a methyl group, L ₆ represents a single bond or a divalent linking group, and R ^3a represents a hydrogen atom or a methyl group.
In the general formula (P-3-r2), M ₃ represents a hydrogen atom or a methyl group, and L ₆ represents a single bond or a divalent linking group.

The L ₆ in the general formula (P-3-r1) and (P-3-r2) is the same as the L ₆ in the above-mentioned general formula (P-3).

Specific examples of the (meth) acrylic polymer (SA) are shown below, but the present invention is not limited thereto.

<Manufacturing method of (meth) acrylic polymer (SA)>
The method for producing the (meth) acrylic polymer (SA) is not particularly limited, and the (meth) acrylic polymer (SA) can be produced by using a known production method. For example, it is produced by a method of radically polymerizing a monomer having a (meth) acryloyl group. can. Examples of the monomer having a (meth) acryloyl group ((meth) acrylate monomer) include a (meth) acrylate monomer having a group containing a fluorine atom (preferably a compound represented by the following general formula (Pd-1)). A (meth) acrylate monomer having a cationically polymerizable group (preferably a compound represented by the following general formula (Pd-2)) and a (meth) acrylate monomer having a radically polymerizable group (preferably the following general formula (Pd-)). It is preferable to use the compound) represented by 3).
The compound represented by the following general formula (Pd-1) corresponds to the structural unit represented by the above general formula (P-1), and the compound represented by the following general formula (Pd-2) corresponds to the above general formula (Pd-2). The compound represented by the following general formula (Pd-3) corresponds to the structural unit represented by the above general formula (P-3).

In the general formula (Pd-1), M ₁ represents a hydrogen atom or a methyl group, L ₄ represents a single bond or a divalent linking group, and Q ₄ represents a group containing a fluorine atom.
In the general formula (Pd-2), M ₂ represents a hydrogen atom or a methyl group, L ₅ represents a single bond or a divalent linking group, and Q ₅ represents a cationically polymerizable group.
In the general formula (Pd-3), M ₃ represents a hydrogen atom or a methyl group, L ₆ represents a single bond or a divalent linking group, and Q ₆ represents a radically polymerizable group.

M ₁ , L ₄ and Q ₄ in the general formula (Pd-1) are synonymous with M ₁ , L ₄ and Q ₄ in the general formula (P-1), respectively, and the preferable range is also the same.
M ₂ , L ₅ and Q ₅ in the general formula (Pd-2) are synonymous with M ₂ , L ₅ and Q ₅ in the general formula (P-2), respectively, and the preferable range is also the same.
M ₃ , L ₆ and Q ₆ in the general formula (Pd-3) are synonymous with M ₃ , L ₆ and Q ₆ in the general formula (P-3), respectively, and the preferable range is also the same.

(Cationic polymerization initiator)
The composition for forming a hard coat layer in the present invention preferably contains a cationic polymerization initiator.
The composition for forming a hard coat layer in the present invention can satisfactorily proceed with the polymerization reaction of the cationically polymerizable groups of the polyorganosylsesquioxane (a1) and the polymer (S) by containing the cationic polymerization initiator. The polyorganosylsesquioxane (a1) and the polymer (S) can be bonded to each other in the hard coat layer.
Only one type of cationic polymerization initiator may be used, or two or more types having different structures may be used in combination. Further, the cationic polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.
The content of the cationic polymerization initiator in the composition for forming a hard coat layer is not particularly limited, but is, for example, 0.1 to 200 mass with respect to 100 parts by mass of polyorganosylsesquioxane (a1). Parts are preferable, and 1 to 50 parts by mass are more preferable.

(solvent)
The composition for forming a hard coat layer 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 composition for forming a hard coat layer in the present invention can be appropriately adjusted within a range in which the coating suitability of the composition for forming a hard coat layer 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 composition for forming a hard coat layer.
The composition for forming a hardcourt layer usually takes the form of a liquid.
The concentration of the solid content of the composition for forming a hard coat layer 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 composition for forming a hard coat layer in the present invention may contain components other than the above, and for example, inorganic fine particles, dispersants, leveling agents, antifouling agents, antistatic agents, ultraviolet absorbers, and antioxidants. Etc. may be contained.

The composition for forming a hard coat layer 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 composition for forming hard coat layer)
The hardcourt layer of the laminate of the present invention contains a cured product of a composition for forming a hardcoat layer containing polyorganosylsesquioxane (a1) and a polymer (S), and is preferably polyorganosylsesqui. It contains a cured product of a hardcourt layer forming composition containing an oxane (a1), a polymer (S) and a cationic polymerization initiator.
The cured product of the composition for forming a hard coat layer is at least a cured product obtained by bonding the cationically polymerizable group of polyorganosylsesquioxane (a1) and the cationically polymerizable group of the polymer (S) by a polymerization reaction. It is preferable to include it.
The content of the cured product of the composition for forming the hard coat layer in the hard coat layer of the laminate of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass. % Or more is more preferable.

(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 laminated body 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 laminate of the present invention includes a scratch resistant layer.
The scratch resistant layer is formed on the hard coat layer.
The laminate of the present invention has at least one scratch resistant layer on the surface of the hardcoat layer opposite to the substrate.
The scratch-resistant layer of the laminate of the present invention 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.
The 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, an allyl group and the like, 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, hydroxypivalate neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( Meta) acrylate, dicyclopentanyldi (meth) acrylate and the like are preferably exemplified.
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. Examples thereof include erythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexa (meth) acrylate, but in terms of high cross-linking, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol. Pentaacrylates, dipentaerythritol hexaacrylates, or mixtures thereof are preferred.

Only one kind of compound (c1) may be used, or two or more kinds 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.
The scratch-resistant layer forming composition in the present invention contains a radical polymerization initiator, and thus a polymerization reaction of the radically polymerizable groups of the polymer (S) and the compound (c1) contained in the above-mentioned hard coat layer forming composition. The polymer (S) unevenly distributed on the surface of the hard coat layer coating on the scratch resistant layer coating side and the compound (c1) in the scratch resistant layer coating can be bonded. It is possible to improve the adhesion between the hard coat layer and the scratch resistant layer.
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. Up to 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 composition for forming a hard coat layer.
The content of the solvent in the scratch-resistant layer-forming composition in the present invention can be appropriately adjusted as long as 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 polyfunctional (meth) acrylate 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, dilated and additive polymerizable, as an example of a preferable substituent. Examples include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a cinnamoyle group, an epoxy group, an oxetanyl group, a hydroxyl group, a polyoxyalkylene group, a carboxyl group and an 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 is a (per) fluoroalkyl group or (per) fluoropolyether group, W is a single bond or a linking group, ^RA is a polymerizable unsaturated group, and nf is 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, preferably (meth). Examples include an acryloyl group, a (meth) acryloyloxy group, a vinyl group, an allyl group, etc., a (meth) acryloyl group, a (meth) acryloyloxy group, and a group in which any hydrogen atom in these groups is substituted with a fluorine atom. 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 (per) 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 (eg, -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 ). Even with ₅ CF _2H ), it has an alicyclic structure (preferably a 5-membered ring or a 6-membered ring, for example, a perfluorocyclohexyl group and a perfluorocyclopentyl group, and an alkyl group 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 fluorine 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.
The above pf and qf each 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 is particularly preferably having a perfluoropolyether group represented by − (CF ₂ O) _pf − (CF ₂ CF ₂ O) _qf −.

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

In the general formula (F), W represents a linking group. Examples of W include 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 and the like, and a functional group in which these groups are combined.
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, still 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 Industries, Ltd., 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 the 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 scratch-resistant layer forming composition. 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 laminate of the present invention contains a cured product of the composition for forming a scratch-resistant layer containing the compound (c1), and is preferably a scratch-resistant layer containing the compound (c1) and a radical polymerization initiator. It contains a cured product of the 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 laminate of the present invention is preferably 60% by mass or more, more preferably 70% by mass or more, based on the total mass of the scratch-resistant layer. It is preferable, and 80% by mass or more is more 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 more preferably 0.1 to 1.0 μm from the viewpoint of repeated bending resistance. More preferred.

<Repeat bending resistance>
The laminate of the present invention has excellent repeated bending resistance.
In the laminated body of the present invention, cracks do not occur when the 180 ° bending test is repeated 300,000 times with a radius of curvature of 2 mm with the scratch resistant layer 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 laminate 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 test is repeatedly performed with the scratch resistant layer inside (base material on the outside). The above tester bends 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 center of 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 300,000 times.

A laminate having a base material, a hard coat layer, and a scratch resistant layer in this order, wherein the hard coat layer contains the above-mentioned polyorganosylsesquioxane (a1) and a polymer (S). The scratch-resistant layer contains the cured product of the layer-forming composition, and the scratch-resistant layer is a laminate containing the cured product of the scratch-resistant layer-forming composition containing the radically polymerizable compound (c1). It can be an excellent laminated body.

<Scratch resistance>
The laminate of the present invention has excellent scratch resistance.
The laminate of the present invention does not cause scratches when the surface of the scratch-resistant layer is rubbed 100 times reciprocatingly while applying a load of 1 kg / cm ² with # 0000 steel wool, and is rubbed 1000 times reciprocatingly. It is preferable that no scratches occur in some cases.
The scratch resistance is specifically measured as follows.
The surface of the scratch-resistant layer of the laminated body is subjected to a rubbing test under the following conditions using a rubbing tester to obtain an index of scratch resistance.
Evaluation environmental conditions: 25 ° C, relative humidity 60%
Rubbing material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., grade No. # 0000)
Wrap it around the rubbing tip (2 cm x 2 cm) of the tester that comes into contact with the sample, and fix the band. Movement distance (one way): 13 cm,
Rubbing speed: 13 cm / sec,
Load: 1 kg / cm ²
Tip contact area: 2 cm x 2 cm
Number of rubs: 10 round trips, 100 round trips, 1000 round trips Apply oil-based black ink to the surface (surface of the base material) opposite to the rubbed surface (scratch resistant layer surface) of the laminated body after the test, and reflect it. Visually observe with light to measure and evaluate the number of times of rubbing when scratches occur on the part that was in contact with steel wool.

A laminate having a base material, a hard coat layer, and a scratch resistant layer in this order, wherein the hard coat layer contains the above-mentioned polyorganosylsesquioxane (a1) and a polymer (S). The scratch-resistant layer contains a cured product of the layer-forming composition, and the scratch-resistant layer is a laminate containing a cured product of the scratch-resistant layer-forming composition containing a radically polymerizable compound (c1). It can be an excellent laminated body.

<Manufacturing method of laminated body>
The method for manufacturing the laminated body of the present invention will be described.
The method for producing the laminate of the present invention is preferably a production method including the following steps (I) to (IV).
(I) On the substrate, a polyorganosylsesquioxane (a1) having a cationically polymerizable group and a polymer (S) having a group containing a fluorine atom, a cationically polymerizable group and a radically polymerizable group are placed. Step of applying the containing composition for forming a hard coat layer to form a hard coat layer coating film (II) Step of forming a hard coat layer by curing the above hard coat layer coating film (III) On the above hard coat layer A step of applying a scratch-resistant layer forming composition containing a radically polymerizable compound (c1) to form a scratch-resistant layer coating film (IV) A scratch-resistant layer is formed by curing the scratch-resistant layer coating film. Process to do

-Step (I)-
In the step (I), the polyorganosylsesquioxane (a1) having a cationically polymerizable group on the substrate and the polymer (S) having a group containing a fluorine atom, a cationically polymerizable group and a radically polymerizable group are used. This is a step of applying a composition for forming a hard coat layer containing) to form a hard coat layer coating film.
The base material, polyorganosyl sesquioxane (a1), polymer (S) and composition for forming a hard coat layer are as described above.

The method for applying the composition for forming a hard coat layer 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 hardcourt layer coating means polymerizing at least a part of the cationically polymerizable groups of the polyorganosylsesquioxane (a1) and the polymer (S) contained in the hardcoat layer coating. ..

Hardcoat layer The coating film is preferably cured 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 semi-cure the curable compound by irradiating an ultraviolet lamp with an irradiation amount of 10 mJ / cm ² to 2000 mJ / cm ² . It is more preferably 50 mJ / cm ² to 1800 mJ / cm ² , and even more preferably 100 mJ / cm ² to 1500 mJ / cm ² . As the ultraviolet lamp type, a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used.

When it is cured by heat, the temperature is not particularly limited, but it 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)-
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 composition for forming a scratch-resistant layer 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. 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, it is preferable to semi-cure the hardcourt 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 the 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 that only a part of the cationically polymerizable groups of the polyorganosyl sesquioxane (a1) and the polymer (S) contained in the hard coat layer coating film is polymerized. It means to let you. Semi-curing of the hardcourt layer coating film can be performed by adjusting the irradiation amount of ionizing radiation and the temperature and time of heating.

Drying treatment, if necessary, 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 treatment 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 hot air or the atmospheric temperature in the heating furnace.

The laminate of the present invention is excellent in scratch resistance and repeated bending resistance and has little whitening, and can be used as, for example, an optical film (preferably a hard coat film). Further, the laminate of the present invention can be used as a surface protective film for an image display device, and can be used, for example, as a surface protective film for a foldable device (foldable display). A foldable device is a device that employs a flexible display whose display screen is deformable, and it is possible to fold the device body (display) by utilizing the deformability of the display screen.
Examples of the foldable device include an organic electroluminescence device and the like.

The present invention also relates to an article provided with the laminate of the present invention and an image display device provided with the laminate of the present invention as a surface protective film.

Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not 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, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler, the temperature of the reactor was changed to 25. It was set to ℃. To this, 64.0406 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 acid 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 dried in 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% by 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 the cooled film was separated from the frame, it was further heat-treated at 300 ° C. for 30 minutes as a final heat treatment step to obtain a substrate S-1 having a thickness of 30 μm and made of a polyimide film.

<Synthesis of polyorganosyl sesquioxane (a1)>
(Synthesis of compound (A))
In a 1000 ml flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen introduction tube, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 300 mmol (73. 9 g), 7.39 g of triethylamine, and 370 g of MIBK (methyl isobutyl ketone) were mixed, and 73.9 g of pure water was added dropwise over 30 minutes using a dropping funnel. This reaction solution was heated to 80 ° C., and the polycondensation reaction was carried out under a nitrogen stream for 10 hours.
Then, the reaction solution was cooled, 300 g of 5 mass% saline was added, and the organic layer was extracted. The organic layer was washed twice with 300 g of 5 mass% saline solution and 300 g of pure water, and then concentrated under the conditions of 1 mmHg and 50 ° C. to form a colorless and transparent liquid as a MIBK solution having a solid content concentration of 59.8 mass%. A compound (A) which is a polyorganosylsesquioxane (a1) having an alicyclic epoxy group (Rb: 2- (3,4-epoxycyclohexyl) ethyl group in the general formula (1), q = 100. , R = 0 compound)} was obtained in an amount of 87.0 g.
Analysis of the product revealed a number average molecular weight of 2050 and a molecular weight dispersion of 1.9.
In addition, 1 mmHg is about 133.322 Pa.

<Synthesis of polymer (S)>
(Synthesis of polymer represented by (SX1-1))
Trimethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane 30 mmol (14.05 g), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 135 mmol (33.26 g), acrylic Mix 135 mmol (31.63 g) of 3- (trimethoxysilyl) propyl acid, 7.39 g of triethylamine, and 370 g of MIBK (methyl isobutyl ketone), and add 73.9 g of pure water over 30 minutes using a dropping funnel. Dropped. This reaction solution was heated to 50 ° C. and a polycondensation reaction was carried out for 10 hours.
Then, the reaction solution was cooled, 300 g of 5 mass% saline was added, and the organic layer was extracted. The organic layer was washed twice with 300 g of 5 mass% saline solution and 300 g of pure water, and then concentrated under the conditions of 30 mmHg and 50 ° C. to form a colorless and transparent liquid product as a MIBK solution having a solid content concentration of 52 mass%. A polymer (polyorganosylsesquioxane) represented by the following formula (SX1-1) was obtained.

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 H NMR (400 MHz, CDCl ₃ , ppm): δ6.3-6.5 (m, (III) acrylic part CH ₂ = CHCO ₂ ), δ6.0-6.2 (m, (III) acrylic part CH ₂ = CHCO ₂ ), δ5.7-5.9 (m, (III) acrylic part CH ₂ = CHCO ₂ ), δ4.0-4.2 (m, (III) next to the acrylic part CH ₂ = CHCO ₂ CH ₂ ), δ3.0-3.2 (m, (II) Epoxy part CHOCH), δ1.8-2.3 (m, (I) Next to fluorine C ₆ F ₁₃ CH ₂ CH ₂ ), δ1. 6-1.8 (m, (III) CH ₂ Si next to the silyl group), δ1.0-1.5 (m, (II) alicyclic part C 6H ₆ ), _δ0.8-1.0 ( m, (I) adjacent to the silyl group C ₆ F ₁₃ CH ₂ CH ₂ Si), δ0.4-0.8 (m, (II) & (III) methylene moiety CH ₂ CH ₂ CH ₂ Si).

In the synthesis of the polymer represented by the above (SX1-1), the polymer ((SX1-2), (SX1-3), in which the molar content ratio of each structural unit is changed by changing the amount of each monomer used, (SX1-4), (SX1-5), (SX1-R1), (SX1-R2), (SX1-R3)) were synthesized.

In the synthesis of the polymer represented by the above (SX1-1), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was changed to 3-glycidyloxypropyltrimethoxysilane, and the amount of each monomer used was further changed. Then, the polymer represented by (SX4-1) was synthesized.

In the synthesis of the polymer represented by the above (SX1-1), 3- (trimethoxysilyl) propyl acrylate was changed to 3- (trimethoxysilyl) octyl acrylate, and the amount of each monomer used was further changed. , (SX5-1) was synthesized.

In the synthesis of the polymer represented by the above (SX1-1), trimethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane is replaced with trimethoxy (1H, 1H, 2H, 2H-nonafluoro-n-hexyl). ) The polymer represented by (SX2-1) was synthesized by changing to silane and further changing the amount of each monomer used.

In the synthesis of the polymer represented by the above (SX1-1), trimethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane is used as trimethoxy (1H, 1H, 2H, 2H-heptadecafluoro-n). -Decil) Silane was changed, and the amount of each monomer used was further changed to synthesize the polymer represented by (SX3-1).
The structure of each polymer used as the interlayer adhesion agent is shown below. The molecular weight (Mw) and dispersity (Mw / Mn) of each polymer are shown in Table 1 below. In the following structural formula, "SiO _1.5 " represents a silsesquioxane unit.

[Example 1]
<Preparation of composition for forming a hard coat layer>
(Composition for forming a hard coat layer HC-1)
An interlayer adhesion agent (SX1-1), CPI-110P, and MIBK (methyl isobutyl ketone) are added to the MIBK solution containing the compound (A), and the content of each component is adjusted as follows. It was put into a mixing tank and stirred. The obtained composition was filtered through a polypropylene filter having a pore size of 0.45 μm to obtain a hardcourt layer forming composition HC-1.

MIBK solution of compound (A) (solid content concentration 59.8% by mass)
82.1 parts by mass MIBK solution of interlayer adhesion agent (SX1-1) (solid content concentration 52% by mass)
0.2 parts by mass CPI-110P 13.0 parts by mass MIBK 4.6 parts by mass

CPI-110P is a photocationic polymerization initiator (solid content concentration 50% by mass) manufactured by San-Apro Co., Ltd.

<Preparation of composition for forming a scratch-resistant layer>
(Composition SR-1 for forming a scratch-resistant layer)
Each component was charged into a mixing tank with the composition described below, stirred, and filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a scratch-resistant layer forming composition SR-1.
DPHA 96.2 parts by mass Irgacure 127 2.8 parts by mass RS-90 1.0 part by mass Methyl ethyl ketone 300.0 parts by mass

The compounds used in the scratch-resistant layer forming composition are as follows.
DPHA: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Irgacure 127 (Irg.127) manufactured by Nippon Kayaku Co., Ltd .: Radical photopolymerization initiator, RS-90: Sliding agent manufactured by BASF, DIC Co., Ltd. ) Made

(Manufacturing of laminated body (hard coat film))
The hardcourt layer forming composition HC-1 is applied onto a polyimide substrate S-1 having a thickness of 30 μm using a wire bar # 18 so that the film thickness after curing is 18 μm, and the bar is applied onto the substrate. A hard coat layer coating film was provided on the surface.
Next, after drying the hard coat layer coating film at 120 ° C. for 1 minute, an illuminance of 18 mW / cm ² and an irradiation amount of 19 mJ / cm were used under the conditions of 25 ° C. and an oxygen concentration of 100 ppm (parts per million) using an air-cooled mercury lamp. The ultraviolet rays of ² were irradiated. In this way, the hard coat layer coating film was semi-cured.
Then, the scratch-resistant layer forming composition SR-1 was applied onto the semi-cured hard coat layer coating film using a die coater so that the cured film thickness was 0.8 μm.
Next, the obtained laminate was dried at 120 ° C. for 1 minute, and then irradiated with ultraviolet rays at 25 ° C., an oxygen concentration of 100 ppm, an illuminance of 60 mW / cm ² , and an irradiation amount of 600 mJ / cm ² , and further irradiated with ultraviolet rays at 80 ° C. and an oxygen concentration of 100 ppm. The hard coat layer coating film and the scratch resistant layer coating film were completely cured by irradiating with ultraviolet rays having an illuminance of 60 mW / cm ² and an irradiation dose of 600 mJ / cm ² using an air-cooled mercury lamp under the conditions.
Then, the obtained laminate was heat-treated at 120 ° C. for 1 hour to obtain the laminate (hardcoat film) of Example 1 having a hardcoat layer and a scratch resistant layer on the substrate.

[Examples 2 to 10, Comparative Examples 1 to 7]
Examples 2 to 10 are the same as in Example 1 except that the type and content of the interlayer adhesion agent used, the film thickness of the hard coat layer, and the film thickness of the scratch resistant layer are changed as described in Table 1 below. , The laminated bodies (hard coat film) of Comparative Examples 1 to 7 were produced.

[Evaluation of laminated body (hard coat film)]
The manufactured laminates (hard coat films) of Examples and Comparative Examples were evaluated by the following methods.

(Scratch resistance)
The surface of the scratch-resistant layer of the laminated body (hard coat film) of each of the manufactured Examples and Comparative Examples was subjected to a rubbing test under the following conditions using a rubbing tester to obtain an index of scratch resistance.
Evaluation environmental conditions: 25 ° C, relative humidity 60%
Rubbing material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., grade No. # 0000)
Wrap it around the rubbing tip (2 cm x 2 cm) of the tester that comes into contact with the sample, and fix the band. Movement distance (one way): 13 cm,
Rubbing speed: 13 cm / sec,
Load: 1 kg / cm ²
Tip contact area: 2 cm x 2 cm
Number of rubs: 10 round trips, 100 round trips, 1000 round trips Apply oil-based black ink to the surface (surface of the base material) opposite to the rubbed surface (scratch resistant layer surface) of the hard coat film after the test. By visually observing with the reflected light, the number of times of rubbing when the part in contact with the steel wool was scratched was measured and evaluated.
A: No scratches when rubbed 1000 times round trip B: No scratches when rubbed 100 times round trip, but scratches occur when rubbed 1000 times round trip C: Scratches occur when rubbed 10 times round trip No, but scratches occur when rubbed 100 times round trip D: Scratches occur when rubbed 10 times round trip

(Repeat bending resistance)
A sample film having a width of 15 mm and a length of 150 mm was cut out from the manufactured laminates (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, using a 180 ° folding resistance tester (IMC-0755 type manufactured by Imoto Seisakusho Co., Ltd.), the bending resistance was repeatedly tested with the scratch resistant layer on the inside (base material on the outside). 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 180 ° bending test was repeated 300,000 times, the one in which no crack was generated was evaluated as A, and the one in which the crack was generated was evaluated as B. The presence or absence of cracks was visually evaluated.

(Whitening of film)
The whitening of the film was evaluated by the surface roughness (Ra) measured using a surface roughness non-contact three-dimensional surface shape measuring device (VertScan (trade name), manufactured by Ryoka System Co., Ltd.).
If the surface Ra is less than 80 nm, A (the film is clearly visible), if the surface Ra is 80 nm to less than 150 nm, B (the film is slightly whitened), and if the surface Ra is 150 nm or more, C (the film is whitened). And said.

In Table 1 below, the content of the interlayer adhesion agent (% by mass) is a value with respect to the total solid content of the composition for forming a hard coat layer.

As shown in Table 1, the laminates (hard coat films) of Examples 1 to 10 were excellent in scratch resistance and repeated bending resistance, and whitening was suppressed.

According to the present invention, it is possible to provide a laminate having excellent scratch resistance and repeated bending resistance and suppressed whitening, an article provided with the laminate, and an image display device.

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 February 27, 2019 (Japanese Patent Application No. 2019-34955), the contents of which are incorporated herein by reference.

Claims (11)

A laminate having a base material, a hard coat layer, and a scratch resistant layer in this order.
The hard coat layer is
A composition for forming a hard coat layer containing a polyorganosylsesquioxane (a1) having a cationically polymerizable group, a group containing a fluorine atom, a cationically polymerizable group, and a polymer (S) having a radically polymerizable group. Including cured products
The scratch-resistant layer contains a cured product of a scratch-resistant layer-forming composition containing a radically polymerizable compound (c1).
When the 180 ° bending test was repeated 300,000 times with the scratch-resistant layer inside and a radius of curvature of 2 mm, no cracks occurred and cracks did not occur.
A laminate that does not cause scratches when the surface of the scratch-resistant layer is rubbed 100 times back and forth while applying a load of 1 kg / cm ² with # 0000 steel wool. The laminate according to claim 1, wherein the polymer (S) is polyorganosyl sesquioxane. The polymer (S) is represented by the following general formula (S-1), the following general formula (S-2), and the following general formula (S-3). The laminate according to claim 2, which has a structural unit.

In the general formula (S-1), L ₁ represents a single bond or a divalent linking group, and Q ₁ represents a group containing a fluorine atom.
In the general formula (S-2), L ₂ represents a single bond or a divalent linking group, and Q ₂ represents a cationically polymerizable group.
In the general formula (S-3), L ₃ represents a single bond or a divalent linking group, and Q ₃ represents a radically polymerizable group. The one according to any one of claims 1 to 3, wherein the content molar ratio of the constituent unit having a fluorine atom in the polymer (S) is more than 1 mol% and 70 mol% or less with respect to all the constituent units. Laminated body. The laminate according to any one of claims 1 to 4, wherein in the polymer (S), the molar content ratio of the structural unit having a radically polymerizable group is more than 1 mol% with respect to all the structural units. .. The laminate according to any one of claims 1 to 5, wherein the scratch-resistant layer has a film thickness of less than 3.0 μm. The laminate according to any one of claims 1 to 6, wherein the substrate contains at least one polymer selected from an imide-based polymer and an aramid-based polymer. The laminate according to any one of claims 1 to 7, wherein the cationically polymerizable group in the polyorganosylsesquioxane (a1) is an epoxy group. Any of claims 1 to 8, wherein the composition for forming a hard coat layer contains the polymer (S) in an amount of 0.001 to 5% by mass based on the total solid content of the composition for forming a hard coat layer. The laminate according to item 1. An article comprising the laminate according to any one of claims 1 to 9. An image display device comprising the laminate according to any one of claims 1 to 9 as a surface protective film.