JP2017114949A - Hard coat coated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat coated film capable of achieving both of excellent scratch resistance and flexibility even with a single layer and excellent in transparency.SOLUTION: The hard coat coated film contains a hard coat layer and having elastic recovery rate Wmeasured by fine hardness test of 0.55 or more and maximum pushing in deformation amount hof 0.20 to 0.50 μm. The structure contains a substrate containing a resin and the hard coat coated film.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a hard coat coating film.

  Since resin materials are excellent in moldability and light weight, multifaceted market development is performed by taking advantage of the features. However, resin materials tend to be inferior in surface hardness, barrier properties, chemical resistance, flame retardancy, heat resistance, and the like as compared with inorganic materials such as metals and glass. Among these, the hardness of the resin material is significantly lower than that of inorganic glass, and the surface is easily damaged, so that there is a problem that practical development is greatly restricted.

  Therefore, in recent years, a hard coat material has been proposed in which an organic / inorganic composite composition is applied to a resin base material and develops strength (abrasion) similar to that of inorganic glass (see, for example, Patent Documents 1 and 2).

JP 2014-109712 A JP 2009-276511 A

  The technique of Patent Document 1 uses an active energy ray-curable resin composition (such as a polyfunctional acrylate resin composition) as a hard coat film. The acrylate resin has a high hardness and is excellent in scratching property, but has a problem that the flexibility of the base material is impaired.

  The technique of patent document 2 uses a silicone polymer as a hard coat coating film. In this technology, since the silicone polymer does not have sufficient hardness, the scratch resistance is not sufficient, and since it has a multilayer structure that requires a primer layer between the hard coat film and the substrate, the hard coat There is a problem of complicated processing.

  As described above, in the techniques described in Patent Documents 1 and 2, a hard coat coating film that imparts scratching properties to a substrate such as a resin material, and a hard coat coating film that achieves both scratchability and flexibility in a single layer. Can't get.

  The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a hard coat coating film that can achieve both excellent scratch resistance and flexibility even in a single layer and is excellent in transparency. To do.

As a result of intensive studies in view of the above circumstances, the present invention solves the above problems by providing a hard coat coating film in which the elastic recovery rate W _ER and the maximum indentation deformation amount h _max measured from a microhardness test are in a predetermined range. As a result, the present invention has been completed.

That is, the present invention is as follows.
[1]
Including a hard coat layer,
A hard coat coating film having an elastic recovery rate W _ER measured from a microhardness test of 0.55 or more and a maximum indentation deformation amount h _max of 0.20 to 0.50 μm.
[2]
The hard coat coating film according to [1], wherein the amount of change in haze shown below is 5.0 or less.
<Haze change>
The haze value (H ₀ ) of the hard coat coating film before the steel wool test described below is measured by the method specified in JIS K7136. Further, as a steel wool test, the hard coat coating film is rubbed 5 times back and forth using steel wool (# 0) at a pressure of 130 to 150 gf / cm ² and a speed of about 1 cm / sec. After removing the steel wool powder generated on the surface by the steel wool test, the haze value is measured again (H ₁ ). The difference in haze before and after the steel wool test (H ₁ −H ₀ ) is defined as the amount of change in haze.
[3]
The hard coat coating film according to [1] or [2], wherein the thickness is 200 μm or less.
[4]
The hard coat coating film according to any one of [1] to [3], further comprising an adhesive layer formed on at least one surface of the hard coat layer.
[5]
The hard coat coating film according to any one of [1] to [4], wherein the hard coat layer contains an inorganic oxide (A).
[6]
The hard coat coating film according to [5], wherein the inorganic oxide (A) is silica.
[7]
The hard coat coating film according to any one of [1] to [6], wherein the hard coat layer contains a hydrolyzable silicon compound (B).
[8]
The hard coat coating film according to [7], wherein the hydrolyzable silicon compound (B) is a polyfunctional silane having 3 to 20 atomic groups represented by the following formula (b1) in one molecule.
R ¹ _n SiX _3-n A- (b1)
(In the formula, R ¹ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group. On these substituents, a halogen group, a hydroxy group, a mercapto group, an amino group, (meta ) It may have an acryloyl group or an epoxy group, X represents a hydrolyzable group, n is an integer of 0 to 2, A is a site containing 2 to 20 methylene groups, and has a substituent. You may do it.)
[9]
The hard coat coating film according to [7] or [8], wherein the hydrolyzable silicon compound (B) is 35 parts by mass or more with respect to 100 parts by mass of the inorganic oxide (A).
[10]
The hard coat coating film according to any one of [1] to [9], wherein the hard coat layer contains polymer particles (C).
[11]
The hard coat coating film according to [10], wherein the hydrolyzable silicon compound (B) is 35 parts by mass or more with respect to 100 parts by mass of the polymer particles (C).
[12]
The structure containing the base material containing resin, and the hard-coat coating film in any one of [1]-[11].

  According to the present invention, it is possible to provide a hard coat coating film that can achieve both excellent scratchability and flexibility even in a single layer and is excellent in transparency.

It is a Fh curve for demonstrating the elastic recovery factor and the maximum indentation deformation amount in this embodiment. It is a Fh curve which shows the result of having used the coating film which concerns on Example 1 for a micro hardness test. It is a Fh curve which shows the result of having used the coating film which concerns on the comparative example 1 for a micro hardness test.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

The hard coat coating film of the present embodiment includes a hard coat layer, has an elastic recovery rate W _ER measured from a micro hardness test of 0.55 or more, and a maximum indentation deformation amount h _max is 0.20 to 0.00. 50 μm. Since it is comprised in this way, the hard-coat coating film which concerns on this embodiment can be compatible with the abrasion property which was excellent also in the single layer, and the softness | flexibility, and is excellent also in transparency.

[Micro hardness test]
The microhardness test in this embodiment is an indentation test using Fischer scope (model number: H-100CS) manufactured by Fischer Instruments (test condition; indenter: Vickers square pyramid diamond indenter, load condition: 1 mN / 20 sec, creep: 5 sec, unloading condition: −1 mN / 20 sec, measurement load range 0.4 mN to 1 mN, 200 points at equal intervals during loading and unloading, 10 points at equal intervals during creep). This microhardness test evaluates the difficulty (hardness) of deformation from the area or depth of an indentation (dent) formed by applying a constant load, and F (load) -h ( An indentation deformation amount) curve is obtained. Here, in FIG. 1, when the indentation deformation amount of the coating film when the load is continuously applied from 0 (zero) to F with the indenter is the maximum indentation deformation amount h _{max in} this embodiment, the coating film The energy (initial plastic deformation energy: E _{p, initial} ) used for h _max deformation is given by the following equation (1).

Thereafter, when the deformation amount returns to h _min when unloading (load zero), the energy (elastic recovery energy: E _e ) used when the deformation amount returns from h _max to h _min is expressed by the following equation (2). ).

Therefore, the energy E _p finally used for plastic deformation in this micro hardness test is given by the following formula (3).
E _p = E _{p, initial} −E _e (3)

The elastic recovery rate W _ER in the present embodiment indicates a ratio of the energy used for elastic recovery out of the total energy consumed in the micro hardness test, and is given by the following formula (4).
W _ER = E _e / (E _e + E _p ) (4)

Here, the difference between the Martens hardness and Vickers hardness, which are conventional indices of material hardness that can be obtained by the same indentation test, and the elastic recovery rate and the maximum indentation deformation amount in this embodiment will be described. Martens hardness is the material hardness represented by the product of the load F and the maximum indentation deformation h _max in FIG. 1 and has the feature that the hardness of the material can be calculated more easily than the indentation test.・ Because plasticity is not considered, even if the amount of deformation is the same when the same load is applied, it is not possible to determine the difference between a material that recovers from deformation such as rubber and a material that does not recover from deformation such as soft jelly. .

The Vickers hardness is the hardness obtained from the diagonal length of the indentation observed by the microscope attached to the test machine after the indentation test, and is more elastic than the Martens hardness. However, considering the case where F ₂ (h) is not a linear function, the plastic elasticity of the coating is not necessarily reflected in the results, and there is room for improvement in terms of accuracy. It can be said that there is.

  On the other hand, when the hardness is evaluated by the elastic recovery rate and the maximum indentation deformation amount in the present embodiment, for example, if the maximum indentation amount is large even if the elastic recovery rate is similarly high, the material is rubber. If the maximum indentation amount is small, it can be seen that the material is a hard material such as steel metal.

Here, the possible value of the elastic recovery rate W _ER in this embodiment is 0 ≦ W _ER ≦ 1, and from the viewpoint that the hard coat coating film is not scratched (that is, scratch resistance), The elastic recovery rate W _ER is 0.55 or more. If it is within this range, the larger the value, the better. More specifically, the elastic recovery rate W _ER is preferably 0.60 or more, and more preferably 0.65 or more. In addition, the hard coat coating film of the present embodiment has a maximum indentation deformation amount h _max of 0.20 to 0.50, preferably a maximum indentation deformation amount h _max from the viewpoint of impact absorbing ability when subjected to an impact. The maximum indentation deformation h _max is 0.20 to 0.40, more preferably 0.20 to 0.40.

Specifically, the elastic recovery property and the maximum indentation deformation amount of the hard coat coating film are measured by the method described in Examples described later. The elastic recovery rate and the maximum indentation deformation amount are, for example, crosslinking density, type of crosslinking agent, coating film drying and heat treatment temperature / time, addition amount of crosslinking agent, inorganic oxide (A) / hydrolyzable silicon compound It can be adjusted as appropriate depending on the ratio of (B) / polymer particles (C), the particle diameter of each component, the coating thickness, the number of functional groups of the hydrolyzable silicon compound, the length of alkyl groups, and the like. More specifically, for example, increasing the composition ratio of the polymer particles (C) to the inorganic oxide (A) and hydrolyzable silicon compound (B) described later, a polyfunctional hydrolyzable silicon compound (B) ) (Hydrolyzable silicon compound (b2) is preferable to hydrolyzable silicon compound (b3) described later), R in hydrolyzable silicon compound (b2) represented by formula (6) described later By adjusting the carbon number of ² to 1-6, the elastic recovery rate tends to increase. Moreover, decreasing the particle size of the inorganic oxide (A) and the polymer particles (C), increasing the content of the inorganic oxide (A), increasing the film thickness of the hard coat coating, The value of “maximum indentation deformation” tends to decrease by increasing the temperature and time of the heat treatment during the production of the coated film.

The hard coat coating film of this embodiment preferably has a haze change amount shown below of 5.0 or less, more preferably 3.0 or less, and even more preferably 1.5 from the viewpoint of abrasion. It is as follows.
<Haze change>
The haze value (H ₀ ) of the hard coat coating film before the steel wool test described below is measured by the method specified in JIS K7136. Further, as a steel wool test, the hard coat coating film is rubbed 5 times back and forth using steel wool (# 0) at a pressure of 130 to 150 gf / cm ² and a speed of about 1 cm / sec. After removing the steel wool powder generated on the surface by the steel wool test, the haze value is measured again (H ₁ ). The difference in haze before and after the steel wool test (H ₁ −H ₀ ) is defined as the amount of change in haze.

[Thickness of hard coat film]
The hard coat coating film of the present embodiment preferably has a thickness of 0.1 μm to 200 μm, more preferably 1 μm to 150 μm, still more preferably 5 μm to 100 μm, and particularly preferably 5 μm to 50 μm. . When the film thickness is in the range of 0.1 μm to 200 μm, it tends to be able to express better scratching properties without deteriorating optical properties. Here, the film thickness of the hard coat film is determined by sufficiently standing the film in a room of constant temperature and humidity of 50% RH, and then a known film thickness meter (for example, Spectrascope, product number: MHAA-). 100 W).

  The film thickness of the hard coat coating film can be adjusted to the above range by, for example, the solid content of the coating solution, the coating WET film thickness, the coating speed, and the morphology control of the coating film components.

[Layer structure of hard coat film]
The hard coat coating film according to this embodiment may further have an adhesive layer formed on at least one surface of the hard coat layer. As the pressure-sensitive adhesive layer, generally used pressure-sensitive adhesives can be used, and are not particularly limited. Examples thereof include thermoplastic resins, thermosetting resins, rubbers and elastomers. Urethane resins, urethane resins, silicone resins and the like are preferable. Moreover, the said adhesive may contain arbitrary appropriate additives as needed. Examples of additives include, but are not limited to, cross-linking agents, tackifiers, plasticizers, pigments, dyes, fillers, anti-aging agents, conductive materials, ultraviolet absorbers, light stabilizers, release modifiers, softening Agents, surfactants, flame retardants, antioxidants and the like. As crosslinking agents, isocyanate crosslinking agents, epoxy crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, amine crosslinking agents peroxide crosslinking agents, melamine crosslinking agents, urea crosslinking agents , Metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, and the like.

  The thickness of the pressure-sensitive adhesive layer is preferably 0.1 μm to 100 μm, more preferably 0.5 μm to 50 μm.

  Further, the hard coat coating film according to this embodiment may further have a functional layer on at least one surface of the hard coat layer. Examples of the functional layer include, but are not limited to, an antireflection layer, an antifouling layer, a polarizing layer, and an impact absorbing layer.

[Inorganic oxide (A)]
The hard coat layer in this embodiment preferably contains an inorganic oxide (A). When inorganic oxide (A) is included, it contributes to the development of the strength of the coating film. In addition, the hydrophilicity of the hydroxyl group on the surface of the particles expresses adhesion to the substrate and improves the stain resistance of the hard coat coating film. Tend to.

  Specific examples of the inorganic oxide (A) in the present embodiment include, but are not limited to, oxides such as silicon, aluminum, titanium, zirconium, zinc, tin, indium, gallium, germanium, antimony, and molybdenum. . These may be a simple substance or a mixture, but from the viewpoint that the hydrolysis and / or condensation reaction of the hydrolyzable silicon compound (B) described later is gentle and the raw material composition of the hard coat coating is easy to handle. Is preferred, and acidic colloidal silica is more preferred. When colloidal silica is used as the inorganic oxide (A), it is preferably in the state of an aqueous dispersion, and can be used either acidic or basic, and the mixed polymer particles (C) and / or It can select suitably according to the stable area | region of a hydrolyzable silicon compound (B).

  The particle diameter of the inorganic oxide (A) in the present embodiment is preferably 1 to 400 nm, more preferably 1 to 100 nm, still more preferably 5 to 50 nm, and still more preferably 8 to 20 nm. When the particle diameter is 1 nm or more, the storage stability of the raw material composition of the hard coat coating film is good, and when it is 400 nm or less, the transparency tends to be good.

  Although it does not specifically limit as acidic colloidal silica which uses the water suitably used in this embodiment as a dispersion solvent, For example, Nissan Chemical Industries Co., Ltd. Snowtex (trademark) -O, Snowtex-OS is mentioned as a commercial item. Adelite (trademark) AT-20Q manufactured by Asahi Denka Kogyo Co., Ltd., Clevosol (trademark) 20H12 manufactured by Clariant Japan Co., Ltd., and clebosol 30CAL25.

  The basic colloidal silica includes silica stabilized by addition of alkali metal ions, ammonium ions, and amines, and is not particularly limited. For example, SNOWTEX-20, SNOWTEX- manufactured by Nissan Chemical Industries, Ltd. 30, Snowtex-C, Snowtex-C30, Snowtex-CM40, Snowtex-N, Snowtex-N30, Snowtex-K, Snowtex-XL, Snowtex-YL, Snowtex-ZL, Snowtex PS -M, Snowtex PS-L, etc. Adelite AT-20, Adelite AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, Adelite AT-, manufactured by Asahi Denka Kogyo Co., Ltd. 40, Adelite AT-50, etc. Clariant Japan Ltd. Kurebozoru 30R9, Kurebozoru 30R50, such Kurebozoru 50R50, DuPont Ludox (TM) HS-40, Ludox HS-30, and the like Ludox LS and Ludox SM-30.

  Further, colloidal silica using a water-soluble solvent as a dispersion medium is not particularly limited. For example, MA-ST-M (methanol dispersion type having a particle size of 20 to 25 nm), IPA-ST manufactured by Nissan Chemical Industries, Ltd. (Isopropyl alcohol dispersion type with a particle size of 10 to 15 nm), EG-ST (ethylene glycol dispersion type with a particle size of 10 to 15 nm), EG-ST-ZL (ethylene glycol dispersion type with a particle size of 70 to 100 nm), NPC-ST (ethylene glycol monopropyl ether dispersion type having a particle size of 10 to 15 nm) and the like can be mentioned.

  These colloidal silicas may contain an inorganic base (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia) or an organic base (such as tetramethylammonium) as a stabilizer.

  Furthermore, the form of the inorganic oxide (A) in the present embodiment is preferably spherical from the viewpoint of the transparency and hardness of the hard coat coating film.

[Hydrolyzable silicon compound (B)]
The hard coat layer in the present embodiment preferably contains a hydrolyzable silicon compound (B). When the hydrolyzable silicon compound (B) is contained, the hard coat coating gives good elastic recovery and exhibits better scratching properties, and the hard coat coating has chemical resistance, weather resistance, The barrier property tends to be improved.

Although it does not specifically limit as a hydrolysable silicon compound (B), For example, the hydrolysable silicon compound (b1) represented by following formula (5), the hydrolysable silicon compound represented by following formula (6) One or more selected from the group consisting of (b2) and a hydrolyzable silicon compound (b3) represented by the following formula (7) can be used.
R ¹ _n SiX _4-n formula (5)
X ₃ Si—R ² _n —SiX ₃ formula (6)
R ³ — (O—Si (OR ³ ) ₂ ) _n —OR ³ formula (7)

In the above formula (5), R ¹ is a hydrogen atom or a halogen group, hydroxy group, a mercapto group, an amino group, (meth) may have an acryloyl group or an epoxy group, an alkyl having 1 to 10 carbon atoms Represents a group, an alkenyl group, an alkynyl group or an aryl group. X represents a hydrolyzable group, and n is an integer of 0 to 3. The hydrolyzable group is not particularly limited as long as it is a group that generates a hydroxyl group by hydrolysis, and examples thereof include a halogen atom, an alkoxy group, an acyloxy group, an amino group, a phenoxy group, and an oxime group.

In the above formula (6), X represents a hydrolyzable group, R ² represents an alkylene group or a phenylene group having 1 to 6 carbon atoms, n is 0 or 1.

In said formula (7), R < ³ > represents a C1-C6 alkyl group and n is an integer of 2-8.

  Specific examples of the hydrolyzable silicon compounds (b1) and (b2) include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, tetra ( n-butoxy) silane, tetra (i-butoxy) silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane , Methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (triphenoxysilyl) ethane, 1,3-bis (tri Phenoxysilyl) propane, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-hydroxypropyltri Methoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Lan, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraacetoxysilane, tetrakis (trichloroacetoxy) silane, Tetrakis (trifluoroacetoxy) silane, triacetoxysilane, tris (trichloroacetoxy) silane, tris (trifluoroacetoxy) silane, methyltriacetoxysilane, methyltris (trichloroacetoxy) silane, tetrachlorosilane, tetrabromosilane, tetrafluorosilane, Trichlorosilane, tribromosilane, methyltrifluorosilane, tetrakis (methylethylketoxime) silane, tris (methylethylketoxy) Silane, phenyltris (methylethylketoxime) silane, bis (methylethylketoxime) silane, methylbis (methylethylketoxime) silane, hexamethyldisilane, hexamethylcyclotrisilazane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethylsilane Bis (dimethylamino) methylsilane, bis (diethylamino) methylsilane, and the like.

  Specific examples of the hydrolyzable silicon compound (b3) represented by the formula (7) are not limited to the following, but include a partial hydrolysis condensate of tetramethoxysilane (for example, trade name “M” manufactured by Tama Chemical Industries, Ltd.). Silicate 51 ”, trade name“ MSI51 ”manufactured by Colcoat Co., Ltd., trade names“ MS51 ”and“ MS56 ”manufactured by Mitsubishi Chemical Corporation), and a partially hydrolyzed condensate of tetraethoxysilane (trade name“ Tama Chemical Industries ” Silicate 35 ”,“ Silicate 45 ”, trade names“ ES140 ”and“ ES148 ”manufactured by Colcoat Co.), a co-hydrolyzed condensate of tetramethoxysilane and tetraethoxysilane (trade names manufactured by Tama Chemical Co., Ltd.) “FR-3”, a trade name “EMSi48” manufactured by Colcoat Co., Ltd.) and the like.

In this embodiment, from the viewpoint of improving the elastic recovery rate W _ER , the hydrolyzable silicon compound (B) is a polyfunctional silane having 3 to 20 atomic groups represented by the following formula (b1) in one molecule. It is preferable that
R ¹ _n SiX _3-n A- (b1)
(In formula (b1), R ¹ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group, and further a halogen group, a hydroxy group, a mercapto group, or an amino group on these substituents. , (Meth) acryloyl group or epoxy group, X represents a hydrolyzable group, n is an integer of 0 to 2, A is a site containing 2 to 20 methylene groups, It may have a group.)

  In the present embodiment, from the viewpoint of controlling the film formability and the maximum indentation deformation amount, the hydrolyzable silicon compound (B) is 5 parts by mass or more with respect to 100 parts by mass of the inorganic oxide (A) in the hard coat layer. It is preferable that it is contained, More preferably, it is 10 mass parts or more, More preferably, it is 35 mass parts or more.

[Polymer particles (C)]
The hard coat layer in the present embodiment preferably includes polymer particles (C). When the polymer particles (C) are included, the hard coat coating film provides good flexibility, and in particular, there is a tendency to suppress cracks and defects of the coating film that may occur when applied to a resin substrate. The coalesced particles (C) control the interaction (for example, hydrogen bonding) with the inorganic oxide (A), thereby adjusting the plastic deformability of the hard coat coating film and exhibiting adhesiveness with the substrate. Take on.

  The interaction between the polymer particles (C) and the inorganic oxide (A) in the present embodiment is not particularly limited, and examples thereof include a hydrogen bond, a chemical bond, and an ionic bond. Specifically, an ionic bond between the anionic functional group derived from the hydroxyl group of the inorganic oxide (A) and the cationic functional group derived from the amino group of the polymer particle (C), or the polymer particle (C) Hydrogen bonds with amide groups and ether groups, and condensation (chemical bonds) of the hydroxyl groups of the inorganic oxide (A) with the polymerization product of the hydrolyzable metal compound constituting the polymer particles (C), etc. Is mentioned.

  In the present embodiment, from the viewpoint of elastic recoverability, the hard coat layer preferably contains 5 parts by mass or more of hydrolyzable silicon compound (B) with respect to 100 parts by mass of the polymer particles (C). Preferably it is 10 mass parts or more, More preferably, it is 35 mass parts or more.

  The polymer particles (C) in the present embodiment are those constituted by the specific polymers shown below. Examples of the polymer include, but are not limited to, polyurethane, polyester, poly (meth) acrylate, poly (meth) acrylate-silicone copolymer, polyvinyl acetate, polybutadiene, Polymers composed of polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene- (meth) acrylate copolymers, rosin derivatives, alcohol adducts of styrene-maleic anhydride copolymers, etc. Etc.

  The polymer particles (C) preferably contain the following vinyl monomer (c2) as a polymerization monomer from the viewpoint of coating strength and adhesion to the substrate.

  The vinyl monomer (c2) includes a vinyl monomer (c2-2) having a secondary and / or tertiary amide group described later, a vinyl monomer having an amino group, and other copolymerizable with these. The vinyl monomer (c3) may be included.

  Moreover, it is preferable that it is 20 mass% or more in a polymer particle (C) from a viewpoint of forming a uniform coating film, and the mass ratio of the said vinyl monomer (c2) is 40 mass% or more. Is more preferable, and it is further more preferable that it is 50 mass% or more.

  The polymer particles (C) preferably contain a hydrolyzable silicon compound (c1) from the viewpoint of coating film strength, and more preferably secondary and / or 3 as the vinyl monomer (c2). The vinyl monomer (c2-2) having a secondary amide group is preferably included as a polymerization monomer. Specifically, it is obtained by polymerizing a hydrolyzable silicon compound (c1) and a vinyl monomer (c2-2) having a secondary and / or tertiary amide group in the presence of water and an emulsifier. More preferred are polymer emulsion particles.

  The polymer particles (C) may be any one of a mixture of (c1) and (c2-2) polymerized, a mixture of (c1) and (c2-2) polymerized, or a composite. These combinations may be used.

  The polymer particles (C) are obtained by polymerizing a vinyl monomer (c2-3) having an amino group as the vinyl monomer (c2) from the viewpoint of coating strength and adhesiveness to a substrate. It is preferable to include as a body.

As described above, a polymer obtained by polymerizing a hydrolyzable silicon compound (c1) and a vinyl monomer (c2-2) having a secondary and / or tertiary amide group in the presence of water and an emulsifier. The hydrolyzable silicon compound (c1) used in the production of the particles (C) is not limited to the following, but for example, a compound represented by the following formula (8) or a condensation product thereof, silane A coupling agent etc. are mentioned.
SiW _x R _y (8)
(In Formula (8), W is an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group, R represents at least one group selected from the group consisting of amide groups, wherein R represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and a substituted group. Or at least one hydrocarbon group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom X is an integer of 1 or more and 4 or less, and y is an integer of 0 or more and 3 or less, and x + y = 4.

  The silane coupling agent which is an example of the hydrolyzable silicon compound (c1) is a functional group having reactivity with organic substances such as a vinyl polymerizable group, an epoxy group, an amino group, a methacryl group, a mercapto group and an isocyanate group. Is a hydrolyzable silicon compound present in the molecule.

  Examples of the hydrolyzable silicon compound (c1) include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane. Tetraalkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane N-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyl Rimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxy Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, 3-ure Trialkoxysilanes such as idpropyltrimethoxysilane and 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n- Propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di- n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane Dialkoxysilanes such as di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane; trimethylmethoxysilane, trimethyl And monoalkoxysilanes such as ethoxysilane. These hydrolyzable silicon compounds (c1) may be used alone or in a mixture of two or more.

  The hydrolyzable silicon compound (c1) may be used as a condensation product. In such a case, the weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) measurement of the condensation product is preferably 200 to 5000, More preferably, it is 300-1000.

  Among the hydrolyzable silicon compounds (c1) described above, silicon alkoxides having a phenyl group, such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, etc. are excellent in polymerization stability in the presence of water and an emulsifier. Therefore, it is preferable.

  Among the hydrolyzable silicon compounds (c1) described above, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyl Dimethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 2-trimethoxysilyl Silane coupling agents having a vinyl polymerizable group such as ethyl vinyl ether, and silane coupling agents having a thiol group such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane are the above-described secondary and / or Vinyl monomers having a tertiary amide group (c2-2) and the copolymerization or the chain transfer reaction to it is possible to generate a chemical bond.

  The amount of the hydrolyzable silicon compound (c1) used is preferably in the range of 0.005 or more and 0.5 or less as a mass ratio (c1) / (C) to the polymer particles (C) to be obtained.

  The mass of the polymer particles (C) is the above-described vinyl monomer (c2-2) having a secondary and / or tertiary amide group, vinyl polymer (c2-3) having an amino group, and the like. It is assumed that this is the mass of the polymerization product obtained when all the other vinyl monomers (c3) copolymerizable with the polymer and further the hydrolyzable silicon compound (c1) are polymerized.

  As the hydrolyzable silicon compound (c1), it is more preferable to use a silane coupling agent having a vinyl polymerizable group from the viewpoint of the weather resistance of the hard coat coating film of this embodiment.

  The content of the hydrolyzable silicon compound (c1) is preferably 0.01% by mass or more and 50% by mass or less with respect to 100% by mass of the polymer particles (C) from the viewpoint of polymerization stability. 0.1 mass% or more and 30 mass% or less are more preferable.

  Examples of the vinyl monomer (c2-2) having secondary and / or tertiary amide groups used for producing the polymer particles (C) include N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethylmeta Acrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N- Acryloylpyrrolidine, N Methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N, N′-methylenebisacrylamide, N , N′-methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, diacetone methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.

  The amide group of the vinyl monomer (c2-2) that can be used for producing the polymer particles (C) is a secondary and / or tertiary amide group, but a vinyl monomer having a tertiary amide group. It is preferable to use a polymer because the hydrogen bonding property between the obtained polymer particles (C) and the inorganic oxide (A) tends to increase. Among them, in particular, N, N-diethylacrylamide is very excellent in polymerization stability in the presence of water and an emulsifier, and also has hydroxyl groups and inorganic oxides (in the above-described polymerization product of the hydrolyzable silicon compound (c1)). It is more preferable because it can form a strong hydrogen bond with the hydroxyl group of A).

  The amino monomer-containing vinyl monomer (c2-3) used for producing the polymer particles (C) is not limited to the following, but examples thereof include dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate. And dimethylaminoethyl methacrylate quaternized product.

  In addition, as the hydrolyzable silicon compound (c1) described above, in addition to the various compounds described above, a silane coupling agent having a vinyl polymerizable group or a thiol group may be used alone or the above-described silicon alkoxide or other silane couplings. Agents and those mixed or complexed with their condensation products can also be used.

  The polymer particles (C) are composed of a polymerization product of a hydrolyzable silicon compound (c1) and a polymerization product of a vinyl monomer (c2-2) having a secondary and / or tertiary amide group. If they are, they may be complexed by hydrogen bonds or chemical bonds.

  The (c1) and (c2-2) are preferably combined by various bonds such as a hydrogen bond and a chemical bond, but the form and state of the bond are not limited in any way. . Furthermore, the above-described complexation may be performed only on a part of the polymer particles (C).

  As polymer particles (C), a hydrolyzable silicon compound (c1) which is a silane coupling agent having a vinyl polymerizable group or a thiol group, and a vinyl monomer having a secondary and / or tertiary amide group (c2) -2) is preferably used because it can form a hard coat film having further excellent weather resistance, chemical resistance, optical properties, strength and the like.

  The compounding amount of the hydrolyzable silicon compound (c1) which is a silane coupling agent having a vinyl polymerizable group or a thiol group is 100 mass of a vinyl monomer (c2-2) having a secondary and / or tertiary amide group. From the viewpoint of polymerization stability, it is preferably from 0.1 parts by weight to 100 parts by weight, more preferably from 0.5 parts by weight to 50 parts by weight, and more preferably from 0.5 parts by weight to 5 parts by weight with respect to parts. Is more preferable.

  In the hard coat coating film of this embodiment, the vinyl monomer (c2-2) having a secondary and / or tertiary amide group that can be used to obtain the polymer particles (C) can be copolymerized therewith. It can be copolymerized with other vinyl monomers (c3). As a result, the properties of the polymerization product to be generated (glass transition temperature, molecular weight, hydrogen bonding force, polarity, dispersion stability, weather resistance, compatibility with the polymerization product of the hydrolyzable silicon compound (c1), etc.) are further improved. It becomes possible to control effectively, which is preferable.

  The other vinyl monomer (c3) copolymerizable with the vinyl monomer (c2-2) having a secondary and / or tertiary amide group is not limited to the following, but for example, (Meth) acrylic acid ester, aromatic vinyl compound, vinyl cyanide compound, carboxyl group-containing vinyl monomer, hydroxyl group-containing vinyl monomer, epoxy group-containing vinyl monomer, carbonyl group-containing vinyl monomer And monomers containing such functional groups.

  Examples of the (meth) acrylic acid ester include, but are not limited to, for example, a (meth) acrylic acid alkyl ester having 1 to 50 carbon atoms in the alkyl part, and an ethylene oxide group having 1 to 100 carbon atoms. (Poly) oxyethylene di (meth) acrylate etc. are mentioned.

  Examples of (meth) acrylic acid alkyl ester having 1 to 50 carbon atoms in the alkyl part include, but are not limited to, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic. Examples include n-butyl acid, 2-ethylhexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and the like.

  Examples of the (poly) oxyethylene di (meth) acrylate having 1 to 100 ethylene oxide groups include, but are not limited to, ethylene glycol di (meth) acrylate and di (meth) acrylic. Examples include diethylene glycol acid, diethylene glycol methoxy (meth) acrylate, and tetraethylene glycol di (meth) acrylate.

  In the present specification, (meth) acrylic is a simple description of methacrylic or acrylic.

  The amount of the (meth) acrylic acid ester used as the vinyl monomer (c3) (when a plurality of (meth) acrylic acid esters are used, the total amount thereof) constitutes the polymer particles (C). Preferably it is 0-99.9 mass% in all the vinyl monomers, More preferably, it is 5-80 mass%, More preferably, it is 20-50 mass%.

  The aromatic vinyl compound as the vinyl monomer (c3) is not particularly limited, and examples thereof include styrene and vinyl toluene.

  The aromatic vinyl compound is preferably 0 to 99.9% by mass, more preferably 5 to 80% by mass in the total vinyl monomers constituting the polymer particles (C).

  The vinyl cyanide compound as the vinyl monomer (c3) is not particularly limited, and examples thereof include acrylonitrile and methacrylonitrile.

  The vinyl cyanide compound is preferably 0 to 99.9% by mass and more preferably 5 to 80% by mass in the total vinyl monomers constituting the polymer particles (C).

  The carboxyl group-containing vinyl monomer as the vinyl monomer (c3) is not particularly limited. For example, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, anhydrous Mention may be made of maleic acid or half esters of dibasic acids such as itaconic acid and maleic acid. By using these carboxylic acid group-containing vinyl monomers, carboxyl groups can be introduced into the polymer particles (C), and electrostatic repulsion can be provided between the polymer emulsion particles. It tends to improve the stability as an emulsion. As a result, there is a tendency that resistance to an external dispersion breaking action such as agglomeration during stirring is improved. At this time, in order to further improve the electrostatic repulsion force, the introduced carboxyl group is partially or completely neutralized with amines such as ammonia, triethylamine and dimethylethanolamine, and bases such as NaOH and KOH. Also good.

  The amount of the carboxyl group-containing vinyl monomer used (when using a plurality of carboxyl group-containing vinyl monomers, the total amount thereof) is the total vinyl monomers (( In c2) + (c3)), 0 to 50% by mass is preferable from the viewpoint of water resistance. More preferably, it is 0.1-10 mass%, More preferably, it is 0.1-5 mass%.

  The hydroxyl group-containing vinyl monomer as the vinyl monomer (c3) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- Hydroxyalkyl esters of (meth) acrylic acid such as hydroxypropy (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; di-2-hydroxy Hydroxyalkyl esters of fumaric acid such as ethyl fumarate and mono-2-hydroxyethyl monobutyl fumarate; (poly) oxyethylene mono (meth) acrylates having 1 to 100 allyl alcohol and ethylene oxide groups; propylene oxide groups 1 to 1 0 (poly) oxypropylene mono (meth) acrylate; Furthermore, “Placcel FM, FA monomer” (trade name of caprolactone addition monomer manufactured by Daicel Chemical Industries) and other α, β-ethylenic properties And hydroxyalkyl esters of unsaturated carboxylic acids.

  When a hydroxyl group-containing vinyl monomer is used as the vinyl monomer (c3), hydrogen of the inorganic oxide (A) and the vinyl monomer (c2-2) having a secondary and / or tertiary amide group It becomes easy to control the bonding force and the water dispersion stability of the polymer particles (C) tends to be improved.

  The amount of the hydroxyl group-containing vinyl monomer used is preferably 0 to 80% by mass, more preferably 0.1 to 50% by mass, and still more preferably in the total vinyl monomers constituting the polymer particles (C). Is 0.1 to 10% by mass.

  The epoxy group-containing vinyl monomer as the vinyl monomer (c3) is not limited to the following, and examples thereof include a glycidyl group-containing vinyl monomer. Examples of the glycidyl group-containing vinyl monomer include, but are not limited to, glycidyl (meth) acrylate, allyl glycidyl ether, and allyl dimethyl glycidyl ether.

  Examples of the carbonyl-containing vinyl monomer as the vinyl monomer (c3) include, but are not limited to, diacetone acrylamide.

  When the glycidyl group-containing vinyl monomer or the carbonyl group-containing vinyl monomer is used as the vinyl monomer (c3), the polymer particle (C) becomes more reactive, and a hydrazine derivative, By crosslinking with a carboxylic acid derivative, an isocyanate derivative, or the like, a hard coat coating film excellent in solvent resistance and the like tends to be obtained. The amount of the glycidyl group-containing vinyl monomer or carbonyl group-containing vinyl monomer used is preferably 0 to 50% by mass in the total vinyl monomers constituting the polymer particles (C).

  An emulsifier may be used in the synthesis of the polymer particles (C). Examples of the emulsifier include, but are not limited to, alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylenealkylarylsulfuric acid, polyoxyethylene distyrylphenyl ether sulfonic acid. Acidic emulsifiers such as alkali metal (Li, Na, K etc.) salts of acidic emulsifiers, anionic surfactants such as ammonium salts of acidic emulsifiers, fatty acid soaps; alkyltrimethylammonium bromide, alkylpyridinium bromide, imidazolinium laurate Quaternary ammonium salts such as quaternary ammonium salts, pyridinium salts, imidazolinium salt type cationic surfactants; polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene Polyoxypropylene block copolymers, reactive emulsifier having a double bond of nonionic surface active agent and a radical polymerizable polyoxyethylene distyryl phenyl ether, and the like.

  Among these emulsifiers, when a reactive emulsifier having a radical polymerizable double bond is selected, the water dispersion stability of the polymer particles (C) is further improved, and water resistance, chemical resistance, optical properties are improved. Since a coating film excellent in characteristics, strength, and the like can be formed, it is further preferable.

  Examples of the reactive emulsifier having a radical polymerizable double bond include, but are not limited to, a vinyl monomer having a sulfonic acid group or a sulfonate group, and a vinyl monomer having a sulfate group. And alkali metal salts or ammonium salts thereof; vinyl monomers having a nonionic group such as polyoxyethylene; vinyl monomers having a quaternary ammonium salt;

  The salt of a vinyl monomer having a sulfonic acid group or a sulfonate group as the reactive emulsifier is not limited to the following. For example, the reactive emulsifier has a radically polymerizable double bond and has a sulfonic acid group. A partially substituted alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polyalkyl ether group having 2 to 4 carbon atoms, or carbon, partially substituted with a group that is an ammonium salt, sodium salt, or potassium salt A compound having a substituent selected from the group consisting of an aryl group of formula 6 or 10 and a succinic acid group; a vinyl sulfonate compound having a vinyl group to which an ammonium salt, sodium salt or potassium salt of a sulfonic acid group is bonded Etc.

  The compound having a succinic acid group partially substituted with a group that is an ammonium salt, sodium salt or potassium salt of the sulfonic acid group is not limited to the following, but examples include allylsulfosuccinate. Can be mentioned. These can also use a commercial item, and it is not specifically limited, For example, Eleminol JS-2 (brand name) (made by Sanyo Kasei Co., Ltd.), Latemuru S-120, S-180A, or S-180 (brand name) (Manufactured by Kao Corporation).

  As a compound having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms, which is partially substituted by a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group, Although not limited to, for example, Aqualon HS-10 or KH-1025 (trade name) (Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria soap SE-1025N or SR-1025 (trade name) (Asahi) Denka Kogyo Co., Ltd.).

  The vinyl monomer having a nonionic group as the reactive emulsifier is not limited to the following, but for example, α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl]- ω-Hydroxypolyoxyethylene (trade names: Adeka Soap NE-20, NE-30, NE-40, etc., manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene alkylpropenyl phenyl ether (trade name: Aqualon RN-10) , RN-20, RN-30, RN-50, etc., manufactured by Dai-ichi Pharmaceutical Co., Ltd.).

  As the usage-amount of the emulsifier in the case of the synthesis | combination of a polymer particle (C), the inside of the range used as 10 mass parts or less is preferable with respect to 100 mass parts of polymer particles (C) obtained, 0.001-5 mass Within the range of parts is more preferable.

  In the synthesis of the polymer particles (C), a hydrolyzable silicon compound (c1) and a vinyl monomer (c2-2) having a secondary and / or tertiary amide group and other vinyl monomers as required The polymerization of the body (c3) is preferably carried out in the presence of a polymerization catalyst.

  The polymerization catalyst for the hydrolyzable silicon compound (c1) can be appropriately selected according to the components of the monomer used for the polymerization and is not limited to the following. For example, halogenation of hydrochloric acid, hydrofluoric acid, etc. Carboxylic acids such as hydrogen, acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid; sulfonic acids such as sulfuric acid and p-toluenesulfonic acid; alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxy Acidic emulsifiers such as ethylene alkylarylsulfuric acid and polyoxyethylene distyrylphenyl ether sulfonic acid; acidic or weakly acidic inorganic salts, acidic compounds such as phthalic acid, phosphoric acid and nitric acid; sodium hydroxide, potassium hydroxide, Sodium methylate, sodium acetate, tetramethylammonium chloride Basic such as tetramethylammonium hydroxide, tributylamine, diazabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane Compounds: Tin compounds such as dibutyltin octylate and dibutyltin dilaurate are listed. Among these, acidic emulsifiers are preferable from the viewpoint of having an effect as an emulsifier as well as a polymerization catalyst, and alkylbenzenesulfonic acid having 5 to 30 carbon atoms is more preferable.

  As a polymerization catalyst for a vinyl monomer (c2-2) having a secondary and / or tertiary amide group, a radical polymerization catalyst that causes radical polymerization by heat or a reducing substance to cause addition polymerization of the vinyl monomer Although not limited to the following, for example, water-soluble or oil-soluble persulfates, peroxides, azobis compounds and the like can be mentioned, and specific examples of the polymerization catalyst are limited to the following. Although not, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like.

  As a compounding quantity of the polymerization catalyst of the vinyl monomer which has the said secondary and / or tertiary amide group, with respect to 100 mass parts of all the vinyl monomers which comprise polymer particle (C), 0.001- 5 parts by mass is preferred. In addition, from the viewpoint of promoting the polymerization rate and performing polymerization at a low temperature of 70 ° C. or lower, for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalite is combined with a radical polymerization catalyst. Are preferably used.

  As described above, the polymer particles (C) are hydrolyzable silicon compound (c1) and vinyl monomer (c2) having secondary and / or tertiary amide groups in the presence of water and an emulsifier, Furthermore, it can be obtained by polymerization using another vinyl monomer (a3) copolymerizable with the vinyl monomer (c2-2), if necessary, preferably in the presence of a polymerization catalyst. it can.

  Polymerization of the hydrolyzable silicon compound (c1) and the vinyl monomer (c2-2) having a secondary and / or tertiary amide group can be carried out separately, but should be carried out simultaneously. Therefore, it is preferable because a micro organic / inorganic composite by hydrogen bonding or the like can be achieved between the two.

  The number average particle diameter of the polymer particles (C) (primary particle diameter; the number average particle diameter of the primary particles of the polymer particles (C)) is preferably 3 to 800 nm. By adjusting the number average particle diameter of the polymer particles (C) to the above range, a coating film having further excellent weather resistance, chemical resistance, optical properties, antifouling properties, antifogging properties, antistatic properties, etc. Can be formed. Moreover, it is more preferable that the number average particle diameter of the polymer particles (C) is 5 to 100 nm from the viewpoint of improving the transparency of the obtained coating film. More preferably, it is 15-80 nm. The number average particle diameter of the polymer particles (C) can be measured by the method described in the examples described later.

  As a method for obtaining the polymer particles (C) having such a number average particle size, for example, the hydrolyzable silicon compounds (c1) and 2 in the presence of a sufficient amount of water for the emulsifier to form micelles. Polymer particles (C) are synthesized by so-called emulsion polymerization by polymerizing a vinyl monomer (c2-2) having a tertiary and / or tertiary amide group and, if necessary, another vinyl polymer (c3). A method is mentioned.

  The method for emulsion polymerization of the polymer particles (C) is not particularly limited, and examples thereof include a hydrolyzable silicon compound (c1) and a vinyl monomer (c2-2) having a secondary and / or tertiary amide group. The other vinyl monomer (c3) copolymerizable with the vinyl monomer (c2-2) having the secondary and / or tertiary amide group as necessary, or in an emulsified state, Examples of the polymerization method include dropping at once, batchwise, or continuously into a reaction vessel and performing polymerization at a reaction temperature of about 30 to 150 ° C. in the presence of the polymerization catalyst, preferably from atmospheric pressure to 10 MPa as necessary. . You may change a pressure and reaction temperature as needed. The ratio between the total amount of the hydrolyzable silicon compound (a1) and the total vinyl monomer and water is not particularly limited, but the final solid content (the polymer obtained when all the added monomers are polymerized) The value calculated based on the total mass (calculated value) of the vinyl (co) polymer and the hydrolyzable silicon compound (c1) is 0.1 to 70% by mass, preferably 1 It is preferable to set it in a range of ˜55 mass%.

  In carrying out the emulsion polymerization of the polymer particles (C), in order to grow or control the particle diameter of the polymer particles (C), a seed polymerization method is performed in which the emulsion particles are preliminarily present in the aqueous phase for polymerization. Also good. Thereby, polymer emulsion particles having a more uniform particle diameter can be obtained.

  The substance used as the seed (nucleus) is not particularly limited, and a known substance can be used, and can be appropriately selected according to reaction conditions and the like.

  The polymerization reaction may be allowed to proceed in the range of pH in the system of preferably 1.0 to 10.0, more preferably 1.0 to 6.0. The pH can be adjusted using a disodium phosphate, borax, or a pH buffer such as sodium bicarbonate or ammonia.

  In addition to the above, the polymer particles (C) may be obtained by hydrolyzable silicon compound (c1) and secondary and / or 3 in the presence of water, an emulsifier necessary for polymerization, and a solvent as necessary. A method of adding water until the polymerization product becomes an emulsion after polymerizing the vinyl monomer (c2-2) having a secondary amide group may be employed.

  The polymer particles (C) preferably have a core / shell layer structure. Furthermore, the polymer particles (C) preferably have different flexibility in the core layer and the shell layer, and the shell layer has higher hardness than the core layer from the viewpoint of the elasticity of the hard coat coating film. Is more preferable. That is, the core layer is preferably more flexible than the shell layer.

  The hardness of the hard coat coating film can be controlled, for example, by adding a hydrolyzable silicon compound (c1) to the shell layer. That is, the hardness of the hard coat coating is determined by using a hydrolyzable silicon compound (c1-3) containing 3 or more hydrolyzable functional groups as the hydrolyzable silicon compound (c1). Of the hydrolyzable silicon compound (c1-3) containing 3 or more of the above, the vinyl monomer (c2-2) having the secondary and / or tertiary amide group and the total hydrolyzable silicon compound (c1) It can be controlled by defining the mass ratio to the quantity.

  Furthermore, the ratio of the hydrolyzable silicon compound (c1-3) component containing three or more hydrolyzable functional groups in the shell layer is such that the total hydrolyzable silicon compound (c1) and the secondary and / or 3 0.01 <(c1-3) / ((c1) + (c2-2)) <0.20 in terms of mass ratio to the total amount with the vinyl monomer (c2-2) having a secondary amide group 0.1 <(c1-3) / ((c1) + (c2-2)) <0.3 is more preferable. Thereby, it exists in the tendency for the intensity | strength of a hard-coat coating film to improve more.

  Furthermore, for the purpose of improving the strength of the hard coat coating film, the ratio of the hydrolyzable silicon compound (c1-3) component containing three or more hydrolyzable functional groups in the core layer is such that the total hydrolyzable silicon The mass ratio with respect to the total amount of the compound (c1) and the vinyl monomer (c2-2) having the secondary and / or tertiary amide group is (c1-3) / ((c1) + (c2− 2)) It is preferable that ≧ 0.20, and more preferably 0.35 or more.

  From the viewpoint of the strength and optical performance of the hard coat coating film, the mass ratio of the vinyl monomer (c2) contained in the polymer particles (C) is preferably 20% by mass or more, more preferably. Is 40% by mass or more, more preferably 50% by mass or more. As long as it is limited to the vinyl monomer (c2) in the core layer, it is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

  Examples of the hydrolyzable silicon compound (c1-3) containing three or more hydrolyzable functional groups include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetraisopropoxy. Tetraalkoxysilanes such as silane and tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyl Trimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyl Methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyl Triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyl Trimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimeth Sisilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acrylic Oxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisotop Examples include trialkoxysilanes such as lopoxysilane, 3-ureidopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane.

  In the polymer particles (C), depending on the use and usage method, components that are usually added to and blended with paints and molding resins, such as thickeners, leveling agents, thixotropic agents, antifoaming agents, Freezing stabilizer, matting agent, crosslinking reaction catalyst, pigment, curing catalyst, crosslinking agent, filler, anti-skinning agent, dispersant, wetting agent, light stabilizer, antioxidant, UV absorber, rheology control agent, Defoaming agent, film forming aid, rust preventive agent, dye, plasticizer, lubricant, reducing agent, antiseptic agent, antifungal agent, deodorant agent, yellowing preventive agent, antistatic agent or charge control agent, etc. Can be blended.

  In the coating film of this embodiment, when the inorganic oxide (A), the hydrolyzable silicon compound (B), and the polymer particles (C) are included, their presence is observed, for example, by a scanning electron microscope (SEM). Etc. can be confirmed. That is, when the coating film of this embodiment contains the above components (A) to (C), when this is observed with an SEM, a so-called sea-island structure can be typically observed. The sea part observed here may contain an inorganic oxide (A) and a hydrolyzable silicon compound (B). Moreover, a hydrolyzable silicon compound (B) and polymer particle (C) may be contained in an island part. In addition, it is the said sea part and island that the inorganic oxide (A), the hydrolyzable silicon compound (B), and the polymer particles (C) that can be included in the coating film of the present embodiment satisfy the above-described preferable quantitative relationship. This can be confirmed from the fact that the area ratio with respect to the part is 100: 0 to 30:70.

[Base material]
Although it does not specifically limit as a base material with which the hard-coat coating film of this embodiment is apply | coated, From a viewpoint of provision of hard-coat property, it is preferable that it is resin. That is, the structure having the base material containing the resin and the hard coat coating film of the present embodiment has excellent scratching properties, flexibility, and transparency. Although not limited to the following as resin used as a base material, For example, a thermoplastic resin and a thermosetting resin are mentioned. Examples of the thermoplastic resin used as the base material include, but are not limited to, polyethylene, polypropylene, polystyrene, ABS resin, vinyl chloride resin, methyl methacrylate resin, nylon, fluororesin, polycarbonate, and polyester resin. . Moreover, as a thermosetting resin used as a base material, although not limited to the following, a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, an epoxy resin, a silicon resin etc. are mentioned.

[Production method]
The method for producing the hard coat coating film of the present embodiment is not particularly limited. For example, a composition dissolved or dispersed in a solvent such as water is applied to the substrate, and is subjected to heat drying or the like. Can be obtained. In the present embodiment, when the above-described components (A) to (C) are used as a water-based composition, it is not only preferable from the viewpoint of environmental burden, but also sufficient compared to conventional solvent-based coating compositions. It tends to be able to ensure film formability and moldability. Here, as solid content concentration of an aqueous dispersion, Preferably it is 0.01-60 mass%, More preferably, it is 1-40 mass%. The viscosity of the aqueous dispersion is preferably 0.1 to 100,000 mPa · s, preferably 1 to 10,000 mPa · s at 20 ° C. Further, the coating method is not limited to the following, for example, spraying method, flow coating method, brush coating method, dip coating method, spin coating method, screen printing method, casting method, gravure printing method, flexographic printing method Etc. The coated dispersion composition can be dried by heat treatment, ultraviolet irradiation, or the like, preferably at room temperature to 500 ° C, more preferably from 40 ° C to 250 ° C.

[Usage]
The hard coat coating film of this embodiment is a single layer and has excellent optical properties and scratching properties. Accordingly, the use of the hard coat coating film is not particularly limited, and examples thereof include building materials, automobile members, electronic devices, and electrical products. Examples of building material applications include wallpaper skin materials, signboards, glass substitutes, and outer wall material top coats. Examples of automobile members include exterior members such as bumpers and door mirrors, interior members such as center panels and door panels, headlamps, rear lamp members, and glass substitute members. In electrical products, for example, it is preferably used for mobile phones, personal computers, portable game machines and the like. Further, it can also be used as a traffic signal member, a top coat material of a machine / device, or the like.

Hereinafter, the present embodiment will be described with specific examples and comparative examples, but the present embodiment is not limited thereto.
Various physical properties in Synthesis Examples, Examples, and Comparative Examples described later were measured by the following methods.

(1) Average particle diameter [nm]
The inorganic oxide (A) was magnified 50,000 to 100,000 times and adjusted so that 100 to 200 spherical inorganic oxide (A) particles were photographed, and a transmission micrograph was taken. Subsequently, the particle diameters (major axis and minor axis) of each photographed inorganic oxide (A) were measured, and the average value ((major axis + minor axis) / 2) was determined and used as the average particle diameter.

(2) Film thickness [μm]
After the hard coat coating material composition (hereinafter referred to as “coating composition”) applied on the substrate is used as a hard coat coating, the thickness of the hard coat coating is measured with an optical film thickness meter ( It was measured using Spectrascope Co., Ltd., product number: MHAA-100W.

(3) Haze [%]
About the test board (base material and hard coat coating film) manufactured by the Example and comparative example which are mentioned later, by the method prescribed | regulated to JIS K7136 using Nippon Denshoku Industries Co., Ltd. turbidimeter NDH2000, it is haze. (Haze) was measured.

(4) Microhardness test Indentation test using Fischer Instruments (model number: H-100CS) manufactured by Fischer Instruments (Test conditions; Indenter: Vickers square pyramid diamond indenter, Load condition: 1 mN / 20 sec, Creep: 5 sec, Unloading Conditions: −1 mN / 20 sec, measuring load range 0.4 mN to 1 mN, measuring 200 points at equal intervals during loading and unloading, measuring 10 points at equal intervals during creep) The maximum indentation deformation amount h _max and the elastic recovery rate W _ER were calculated by calculating 1) to (4) in the load range of 0.4 mN to 1 mN.

Here, when the indentation deformation amount h _max of the coating film when a load is continuously applied to the coating film from 0 (zero) to F with an indenter, energy used to deform the coating film by h _max (initial value) The plastic deformation energy (E _{p, initial} ) is given by the following formula (1).

After that, if the deformation amount returns to h _min when unloading (zero load), the energy (elastic recovery energy: E _e ) used to return the deformation from h _max ⇒ h _min is expressed by the following equation (2) Given in.

Therefore, the energy E _p finally used for plastic deformation in this micro hardness test is given by the following formula (3).
E _p = E _{p, initial} −E _e (3)

The elastic recovery rate W _ER of the present embodiment indicates the ratio of the energy used for elastic recovery out of the total energy consumed in the micro hardness test, and is given by the following formula (4).
W _ER = E _e / (E _e + E _p ) (4)

(5) Number average particle diameter of polymer emulsion particles The number average particle diameter of the polymer particles (C) produced by the synthesis example described later is a dynamic light scattering particle size distribution measuring device (trade name: Microtrack, manufactured by Nikkiso Co., Ltd.). UPA).

(6) Scratch property The surface of the hard coat film is rubbed by steel wool (# 0) by hand five times, and then the steel wool powder adhered to the surface with tissue paper or dry air is removed. ) Haze [%] ”, the haze of the test plate after the test was measured, and the scratch resistance of the coating film was evaluated as follows from the amount of change in haze before and after the steel wool test. The pressure when rubbed with steel wool was 130 to 150 gf / cm ² , and the speed was about 1 cm / sec.
Haze change ≦ 5.0 ・ ・ ・ Scratch evaluation “○”
Haze change> 5.0: Friction evaluation “×”

[Preparation of polymer emulsion (C)]
Hereinafter, synthesis examples of the polymer particles (C) used in Examples and Comparative Examples described later are described.

<Synthesis of Polymer Emulsion Particle (C-1) Water Dispersion>
A reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device was charged with 410 g of ion exchange water and 22 g of 10% aqueous solution of dodecylbenzenesulfonic acid, and then heated to 80 ° C. with stirring to obtain a mixed solution ( 1) was obtained.
To the obtained mixed liquid (1), a mixed liquid (2) of 65 g of dimethyldimethoxysilane and 37 g of phenyltrimethoxysilane (c1-3) was added as a core layer, while maintaining the temperature in the reaction vessel at 80 ° C. It was dripped over 2 hours and the liquid mixture (3) was obtained.
Thereafter, the mixed liquid (3) was stirred for about 1 hour while the temperature in the reaction vessel was 80 ° C.
Next, 50 g of butyl acrylate, 90 g of diethylacrylamide, 120 g of tetraethoxysilane (c1-3), 50 g of phenyltrimethoxysilane (c1-3), and 3-methacrylic as a shell layer were added to the obtained mixture (3). Mixture (4) of loxypropyltrimethoxysilane (c1-3) 1.3 g, acrylic acid 3 g, reactive emulsifier (trade name “ADEKA rear soap SR-1025”, manufactured by Asahi Denka Co., Ltd., solid content 25 (5% by weight aqueous solution) 8 g, 33 g of 2% by weight aqueous solution of ammonium persulfate, and 1000 g of ion-exchanged water (5) were simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Thus, a mixture (6) was obtained.
Further, as a heat curing, the mixture (6) was stirred for about 2 hours while the temperature in the reaction vessel was 80 ° C.
Thereafter, the mixture (6) was cooled to room temperature, filtered through a 100-mesh wire mesh, the concentration was adjusted with water, and an aqueous dispersion (solid content) of polymer emulsion particles (C-1) having a number average particle diameter of 60 nm. 14% by weight, pH 3.2) was obtained.

<Synthesis of Polymer Emulsion Particle (C-2) Water Dispersion>
A reactor having a reflux condenser, a dripping tank, a thermometer and a stirring device was charged with 1040 g of ion-exchanged water and 60 g of a 10% aqueous solution of dodecylbenzenesulfonic acid (Lypon LH-200, manufactured by Kao Corporation), The mixture (1) was obtained by heating to 80 ° C. with stirring.
To the obtained mixed liquid (1), a mixed liquid (2) of 0.4 g of methyltrimethoxysilane, 17 g of dimethyldimethoxysilane and 11 g of phenyltrimethoxysilane (C1-3) was kept at 80 ° C. in the reaction vessel. In the state which was dripped over about 2 hours, the liquid mixture (3) was obtained.
Thereafter, the mixed liquid (3) was stirred for about 1 hour while the temperature in the reaction vessel was 80 ° C.
Next, 11 g of butyl acrylate, 59 g of diethyl acrylamide, 4 g of acrylic acid, a reactive emulsifier (trade name “Adekaria Soap SR-1025”, manufactured by Asahi Denka Co., Ltd.) was added to the resulting mixture (3) as a shell layer. , 25 g of solid content aqueous solution) 3.0 g, 30 g of 2 mass% aqueous solution of ammonium persulfate, and 900 g of ion-exchanged water (4), about 2 in a state where the temperature in the reaction vessel was kept at 80 ° C. It was dripped simultaneously over time and the mixture (5) was obtained.
Further, as a heat curing, the mixture (5) was stirred for about 2 hours while the temperature in the reaction vessel was 80 ° C.
Thereafter, the mixture (5) was cooled to room temperature, filtered through a 100-mesh wire mesh, the concentration was adjusted with purified water, and an aqueous dispersion (solid content) of polymer emulsion particles (c-2) having a number average particle diameter of 19 nm. 6.2% by mass, pH 3.2) was obtained.

[Example 1]
“C-1” prepared above as the polymer emulsion (C), water-dispersed colloidal silica “A-1” (trade name “Snowtex OXS” (ST-OXS)), Nissan Chemical Industries, Ltd. as the inorganic oxide (A) Co., Ltd., solid content 10 mass%, average particle diameter 5 nm), and hydrolyzed silicon compound (B) as tris- (trimethoxysilylpropyl) isocyanurate (trade name “KBM9659”, manufactured by Shin-Etsu Chemical Co., Ltd.) ) Were mixed at a solid content mass ratio (A: B: C mass ratio) shown in Table 1.
The coating composition obtained as described above was applied to a substrate (polycarbonate plate (product number: 1600, thickness: 2 μm) manufactured by Takiron Co., Ltd.) using a bar coater so that the film thickness was 6.0 μm. Then, it dried for 30 minutes at 130 degreeC, and obtained the hard-coat coating film.
At this time, the composition ratio in the coating film (similar to the mass ratio of each component calculated in terms of solid content of the coating composition) is (A) / (B) / (C) = 100/100/100. It was. The evaluation results are shown in Table 1. In addition, FIG. 2 shows an Fh curve obtained as a result of being subjected to the microhardness test.

[Example 2]
Water-dispersed colloidal silica “A-2” (trade name “Snowtex OS” (ST-OS), manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%, average particle size 8-11 nm as inorganic oxide (A) A hard coat coating film was obtained in the same manner as in Example 1 except that the above was changed. The evaluation results are shown in Table 1.

Example 3
The same procedure as in Example 1 except that 1,6-bis (trimethoxysilyl) hexane (trade name “KBM-3066”, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the hydrolyzable silicon compound (B). A coated film was obtained. The evaluation results are shown in Table 1.

Example 4
A hard coat coating film was obtained in the same manner as in Example 1 except that the polymer particles (C) were not used. The evaluation results are shown in Table 1.

Example 5
A hard coat coating film was obtained in the same manner as in Example 1 except that the polymer emulsion particles (C) were changed to “C-2” adjusted as described above. The evaluation results are shown in Table 1.

Example 6
The hydrolyzable silicon compound (B) was changed to methyltrimethoxysilane (trade name “KBM-13”, manufactured by Shin-Etsu Chemical Co., Ltd.), and the composition ratio of (B) was changed as shown in Table 1. A hard coat film was obtained in the same manner as Example 1 except for the above. The evaluation results are shown in Table 1.

Example 7
The hydrolyzable silicon compound (B) was changed to tetraethoxysilane (trade name “KBE-04”, manufactured by Shin-Etsu Chemical Co., Ltd.), and the composition ratio of (B) was changed as shown in Table 1. Obtained a hard coat film in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 8]
AD-1 (Eastern Japan Paint Super Excel Primer) was applied as a pressure-sensitive adhesive layer on the surface of one side of the same substrate as in Example 1 and dried in an atmosphere of 25 ° C. and 50% RH for 24 hours. . Thereafter, a hard coat coating film was obtained in the same manner as in Example 1 except that the substrate was provided with the pressure-sensitive adhesive layer. The evaluation results are shown in Table 1.

[Comparative Example 1]
Hard coat coating in the same manner as in Example 1 except that 3-glycidoxypropyltrimethoxysilane (trade name “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the hydrolyzable silicon compound (B). A membrane was obtained. The evaluation results are shown in Table 1. In addition, FIG. 3 shows an Fh curve obtained as a result of being subjected to the microhardness test.

Claims (12)

Including a hard coat layer,
A hard coat coating film having an elastic recovery rate W _ER measured from a microhardness test of 0.55 or more and a maximum indentation deformation amount h _max of 0.20 to 0.50 μm. The hard coat coating film of Claim 1 whose haze variation | change_quantity shown below is 5.0 or less.
<Haze change>
The haze value (H ₀ ) of the hard coat coating film before the steel wool test described below is measured by the method specified in JIS K7136. Further, as a steel wool test, the hard coat coating film is rubbed 5 times back and forth using steel wool (# 0) at a pressure of 130 to 150 gf / cm ² and a speed of about 1 cm / sec. After removing the steel wool powder generated on the surface by the steel wool test, the haze value is measured again (H ₁ ). The difference in haze before and after the steel wool test (H ₁ −H ₀ ) is defined as the amount of change in haze.   The hard coat coating film of Claim 1 or 2 whose thickness is 200 micrometers or less.   The hard coat coating film according to any one of claims 1 to 3, further comprising a pressure-sensitive adhesive layer formed on at least one surface of the hard coat layer.   The hard-coat coating film of any one of Claims 1-4 in which the said hard-coat layer contains an inorganic oxide (A).   The hard coat coating film according to claim 5, wherein the inorganic oxide (A) is silica.   The hard-coat coating film of any one of Claims 1-6 in which the said hard-coat layer contains a hydrolysable silicon compound (B). The hard coat coating film according to claim 7, wherein the hydrolyzable silicon compound (B) is a polyfunctional silane having 3 to 20 atomic groups represented by the following formula (b1) in one molecule.
R ¹ _n SiX _3-n A- (b1)
(In the formula, R ¹ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group. On these substituents, a halogen group, a hydroxy group, a mercapto group, an amino group, (meta ) It may have an acryloyl group or an epoxy group, X represents a hydrolyzable group, n is an integer of 0 to 2, A is a site containing 2 to 20 methylene groups, and has a substituent. You may do it.)   The hard coat coating film of Claim 7 or 8 whose said hydrolyzable silicon compound (B) is 35 mass parts or more with respect to 100 mass parts of said inorganic oxides (A).   The hard coat coating film of any one of Claims 1-9 in which the said hard-coat layer contains a polymer particle (C).   The hard coat coating film of Claim 10 whose said hydrolyzable silicon compound (B) is 35 mass parts or more with respect to 100 mass parts of said polymer particles (C).   The structure containing the base material containing resin and the hard-coat coating film of any one of Claims 1-11.