JP2013210976A - Protective body and touch panel module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a protective body capable of suppressing warpage, having excellent scratch resistance, antifouling property and printability.SOLUTION: A protective body comprises: a transparent resin plate; a first hard coat layer formed on one surface side of the transparent resin plate; and a second hard coat layer formed on the other surface side of the transparent resin plate. The first hard coat layer comprises: a polymer including active silica fine particles and a first binder component; and a first surfactant. The second hard coat layer comprises: a polymer including a second binder component; and a second surfactant.

Description

  The present invention relates to a protector that can suppress the occurrence of warping and has good scratch resistance, antifouling properties, and printability.

  For example, tempered glass has been conventionally used for the front plate of a touch panel, but tempered glass has problems such as being heavy and cracking. Therefore, a change from tempered glass to a transparent resin plate has been studied. On the other hand, the transparent resin plate has the advantage of being light and difficult to break, but has the disadvantage that the surface is easily damaged.

  By the way, the technique which forms a hard-coat layer (hardened layer) on the surface of a resin film or a resin sheet, and improves abrasion resistance is known. For example, in Patent Document 1, a hard coat layer in which a hard coat layer made of a cured product of a curable resin composition having reactive silica fine particles, reactive deformed silica fine particles, and a binder component is provided on one side of a transparent substrate film. A film is disclosed. Patent Document 2 discloses a transparent multilayer sheet for a display face plate having an acrylic resin layer on at least one side of a polycarbonate resin substrate sheet and further having a hard coat layer on at least one side of the acrylic resin layer. Patent Document 3 discloses an antiglare film for a display in which at least one resin layer is laminated on a transparent base film, and the uppermost layer is an antiglare layer having irregularities. An antiglare film for display, which has antifouling properties, is disclosed.

JP 2010-102123 A JP 2010-44163 A JP 2009-244898 A

  When a hard coat layer is provided on one surface side of the transparent resin plate, there is a problem that warpage is likely to occur due to differences in expansion coefficients of the transparent resin plate and the hard coat layer, that is, thermal expansion coefficient and hygroscopic expansion coefficient. Furthermore, the protector represented by the front plate of the touch panel is required to have good scratch resistance, antifouling property and printability.

  The present invention has been made in view of the above circumstances, and a main object of the present invention is to provide a protector that can suppress the occurrence of warping and has good scratch resistance, antifouling properties, and printability.

  In order to solve the above problems, in the present invention, the transparent resin plate, the first hard coat layer formed on one surface side of the transparent resin plate, and the other surface side of the transparent resin plate are formed. A second hard coat layer, the first hard coat layer has a polymer containing reactive silica fine particles and a first binder component, and a first surfactant imparting antifouling properties, The second hard coat layer provides a protector comprising a polymer containing a second binder component and a second surfactant imparting printability.

  According to this invention, it can be set as the protector which suppressed generation | occurrence | production of curvature by providing a 1st hard-coat layer and a 2nd hard-coat layer in a transparent resin board. Furthermore, since the first hard coat layer is formed using the reactive silica fine particles and the first surface activity, it is possible to provide a protector with good scratch resistance and antifouling properties. Moreover, since the 2nd hard-coat layer is formed using 2nd surface activity, it can be set as a protector with favorable printability.

  Moreover, in this invention, it has a touchscreen sensor and the protector formed on the said touchscreen sensor, The said protector is a protector mentioned above, The touchscreen module characterized by the above-mentioned is provided.

  According to the present invention, by using the above-described protector, the occurrence of warpage can be suppressed, and a touch panel module having excellent scratch resistance, antifouling properties, and printability can be obtained.

  The protector of the present invention can suppress the occurrence of warping, and has the effect of being excellent in scratch resistance, antifouling properties and printability.

It is a schematic sectional drawing which shows an example of the protector of this invention. It is a schematic sectional drawing which shows the other example of the protector of this invention. It is a schematic sectional drawing which shows an example of the manufacturing method of the protector of this invention. It is a schematic sectional drawing which shows an example of the touchscreen module of this invention.

  Hereinafter, the protector and touch panel module of the present invention will be described in detail.

A. Protective body The protective body of the present invention includes a transparent resin plate, a first hard coat layer formed on one side of the transparent resin plate, and a second hard side formed on the other side of the transparent resin plate. The first hard coat layer has a polymer containing reactive silica fine particles and a first binder component, and a first surfactant that imparts antifouling properties, and the second hard coat layer. The coat layer is characterized by having a polymer containing a second binder component and a second surfactant imparting printability.

  FIG. 1 is a schematic cross-sectional view showing an example of the protector of the present invention. As shown in FIG. 1, the protector of the present invention includes a transparent resin plate 1, a first hard coat layer 2 a formed on one surface side of the transparent resin plate 1, and the other surface side of the transparent resin plate 1. And a second hard coat layer 2b formed on the substrate. The first hard coat layer 2a has a polymer containing reactive silica fine particles and a first binder component, and a first surfactant that imparts antifouling properties. The second hard coat layer 2b has a polymer containing a second binder component, and a second surfactant that imparts printability.

  According to this invention, it can be set as the protector which suppressed generation | occurrence | production of curvature by providing a 1st hard-coat layer and a 2nd hard-coat layer in a transparent resin board. Furthermore, since the first hard coat layer is formed using the reactive silica fine particles and the first surfactant, it is possible to provide a protector with good scratch resistance and antifouling properties. Moreover, since the 2nd hard-coat layer is formed using the 2nd surfactant, it can be set as the protector with favorable printability. Thus, there is an advantage that scratch resistance, antifouling property, and printability can be achieved at the same time by imparting different characteristics to the first hard coat layer and the second hard coat layer while suppressing the occurrence of warpage. .

In the present specification, the first hard coat layer and the second hard coat layer may be collectively referred to as a hard coat layer, and the first curable resin composition and the second curable resin composition may be referred to as a curable resin composition. May be collectively referred to.
In the present specification, (meth) acrylate represents acrylate and / or methacrylate.
In the present specification, the molecular weight means a weight average molecular weight which is a polystyrene conversion value measured by gel permeation chromatography (GPC) when having a molecular weight distribution, and when having no molecular weight distribution, Refers to molecular weight.
In this specification, the average particle diameter of the fine particles refers to a 50% particle diameter (d50 median diameter) when the particles in the solution are measured by a dynamic light scattering method and the particle size distribution is expressed by a cumulative distribution. . The average particle size can be measured using a Microtrac particle size analyzer or a Nanotrac particle size analyzer manufactured by Nikkiso Co., Ltd.
Hereinafter, the protector of this invention is demonstrated for every structure.

1. First Hard Coat Layer In the first hard coat layer of the present invention, the first hard coat layer is a polymer containing reactive silica fine particles and a first binder component, and a first surfactant that imparts antifouling properties. It is what has. Usually, the reactive functional group of the reactive silica fine particle and the reactive functional group of the first binder component are respectively crosslinked between the same or different reactive functional groups to form a polymer. Further, the first surfactant may be a component of the polymer, that is, may be crosslinked with the reactive silica fine particles and the first binder component, or may be dispersed around the polymer. good.

  The 1st hard-coat layer in this invention is a layer which provides hardness higher than the hardness in the surface before a 1st hard-coat layer is formed. The hardness of the first hard coat layer can be evaluated by a pencil hardness test (4.9 N load) specified by JIS K5600-5-4 (1999). For example, the pencil hardness of the first hard coat layer is preferably 5H or more, and more preferably 6H or more. This is because the scratch resistance is further improved. On the other hand, the pencil hardness of the first hard coat layer is preferably 9H or less, for example. This is because if the pencil hardness is too high, brittleness increases, causing warping and cracking.

  The first hard coat layer preferably has a contact angle of water droplets of 90 ° or more, more preferably 100 ° or more, and further preferably 110 ° or more. This is because good antifouling properties can be exhibited. On the other hand, the contact angle of the water droplet is usually 120 ° or less. In addition, the contact angle of a water droplet can be calculated | required by measuring using a contact angle measuring device (Kyowa Interface Science Co., Ltd. product CA-Z type | mold) 30 seconds after dripping a water droplet from a microsyringe.

  Moreover, a 1st hard-coat layer is normally comprised from the hardened | cured material of the 1st curable resin composition containing a reactive silica fine particle, a 1st binder component, and a 1st surfactant. Hereinafter, the first curable resin composition will be described in detail.

(1) Reactive silica fine particles The reactive silica fine particles contained in the first curable resin composition are components that contribute to improving the hardness of the first hard coat layer. The reactive silica fine particles usually have a reactive functional group. As the reactive functional group, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group.

  The reactive silica fine particles may be spherical reactive silica fine particles or irregular reactive silica fine particles, but the latter is preferable. This is because it is easy to improve the hardness of the first hard coat layer. Examples of irregular-shaped reactive silica fine particles include non-spherical reactive silica fine particles and reactive silica fine particles in which a plurality of spherical silicas are bonded by inorganic chemical bonds. The non-spherical reactive silica fine particles mean fine particles having an average value of major axis / minor axis in the range of 1.5 to 10. The average primary particle size of the reactive silica fine particles is preferably in the range of 1 nm to 100 nm, for example. More preferably, it is in the range of 5 nm to 80 nm.

  The ratio of the reactive silica fine particles in the first hard coat layer is preferably in the range of 20% by weight to 80% by weight, for example, and more preferably in the range of 40% by weight to 60% by weight. This is because there is a possibility that sufficient hardness cannot be imparted to the first hard coat layer if the solid content concentration of the reactive silica fine particles is too high or too low.

  The reactive silica fine particles in the present invention are spherical reactive silica fine particles (A) having a reactive functional group a on the particle surface having an average primary particle size of 1 to 100 nm, and an average primary particle size of 1 to 100 nm. It is preferable that 3 to 20 spherical silica fine particles are bonded by an inorganic chemical bond and are at least one of reactive deformed silica fine particles (B) having a reactive functional group b on the surface.

<Reactive silica fine particles (A)>
The average primary particle size of the reactive silica fine particles (A) is 1 nm to 100 nm, but preferably 5 nm to 80 nm. If the average primary particle size of the reactive silica fine particles (A) is too small, it may not contribute to the improvement of the hardness of the first hard coat layer, and the average primary particle size of the reactive silica fine particles (A) is too large. This is because the transparency of the first hard coat layer is lowered, and the transmittance may be deteriorated and haze may be increased.

  The reactive silica fine particles (A) may be used not only having a single average primary particle diameter but also a combination of two or more kinds having different average primary particle diameters. When two or more types are used in combination, the average primary particle size of each particle may be within 1 nm to 100 nm.

  Reactive silica fine particles (A) use solid particles that do not have pores or porous structure inside the particles, such as hollow particles, to improve the hardness. From the point of view, it is preferable.

  The reactive silica fine particles (A) have at least a part of the surface coated with an organic component and have a reactive functional group a introduced by the organic component on the surface. Here, the organic component is a component containing carbon. Moreover, as an aspect in which at least a part of the surface is coated with an organic component, for example, a compound containing an organic component such as a silane coupling agent reacts with a hydroxyl group present on the surface of the silica fine particles to cause a part of the surface A mode in which an organic component is bonded to the surface, or a mode in which a compound containing an organic component having an isocyanate group reacts with a hydroxyl group present on the surface of the silica fine particle, and an organic component is bonded to a part of the surface. Examples include an aspect in which an organic component is attached to an existing hydroxyl group by an interaction such as hydrogen bonding, and an aspect in which one or two or more silica fine particles are contained in a polymer particle.

The coated organic component covers almost the entire particle surface from the viewpoint of improving the hardness of the film (first hard coat layer) by introducing many reactive functional groups onto the surface of the silica fine particles. preferable. From such a viewpoint, the organic component covering the silica fine particles is preferably contained in the reactive silica fine particles (A) at 1.00 × 10 ⁻³ g / m ² or more. In an embodiment in which an organic component is attached or bonded to the surface of the silica fine particles, the organic component covering the silica fine particles is contained in the reactive silica fine particles (A) at 2.00 × 10 ⁻³ g / m ² or more. It is more preferable that the reactive silica fine particles (A) contain 3.50 × 10 ⁻³ g / m ² or more. In the aspect in which the silica particles are contained in the polymer particles, the organic component covering the silica particles is further contained in the reactive silica particles (A) at 3.50 × 10 ⁻³ g / m ² or more. It is particularly preferable that 5.50 × 10 ⁻³ g / m ² or more is contained in the reactive silica fine particles (A).

The ratio of the organic component that is coated is usually a constant value of weight loss when the dry powder is completely burned in air, for example, by thermogravimetric analysis from room temperature to 800 ° C. in air. Can be sought.
In addition, the amount of organic components per unit area can be obtained by the following method. First, a value obtained by dividing the organic component weight by the inorganic component weight (organic component weight / inorganic component weight) is measured by differential thermogravimetric analysis (DTG). Next, the volume of the entire inorganic component is calculated from the inorganic component weight and the specific gravity of the silica fine particles used. Further, assuming that the silica fine particles before coating are spherical, the volume per silica fine particle before coating and the surface area are calculated from the average particle diameter of the silica fine particles before coating. Next, the number of reactive silica fine particles (A) is determined by dividing the volume of the entire inorganic component by the volume per silica fine particle before coating. Further, by dividing the organic component weight by the number of reactive silica fine particles (A), the amount of organic component per reactive silica fine particle (A) is determined. Finally, by dividing the weight of the organic component per reactive silica fine particle (A) by the surface area per silica fine particle before coating, the amount of organic component per unit area can be determined.

As a method for preparing reactive silica fine particles (A) having a reactive functional group a introduced on the surface thereof, the organic component being coated on at least a part of the surface, the reactivity desired to be introduced into the silica fine particles A conventionally known method can be appropriately selected and used depending on the functional group a.
In particular, in the present invention, the organic component to be coated can be contained in the reactive silica fine particles (A) at 1.00 × 10 ⁻³ g / m ² or more per unit area of the silica fine particles before coating. Thus, from the viewpoint of suppressing aggregation of silica fine particles and improving the hardness of the film, it is preferable to select and use any of the following silica fine particles (i) and (ii).
(I) saturated or unsaturated carboxylic acid, acid anhydride, acid chloride, ester and acid amide corresponding to the carboxylic acid, amino acid, imine, nitrile, isonitrile, epoxy compound, amine, β-dicarbonyl compound, silane, And by dispersing silica fine particles in water and / or an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of metal compounds having functional groups. Silica fine particles having a reactive functional group a on the surface.
(Ii) a compound containing a reactive functional group a introduced into silica fine particles before coating, a group represented by the following chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis, and metal oxide fine particles Silica fine particles having a reactive functional group a on the surface, obtained by bonding.
Chemical formula (1)
−Q ¹ −C (= Q ² ) −Q ³ −
In chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), Q ² represents O or S, and Q ³ represents NH or a divalent or higher valent organic group. .

Hereinafter, the reactive silica fine particles (A) preferably used will be described in order.
(I) saturated or unsaturated carboxylic acid, acid anhydride, acid chloride, ester and acid amide corresponding to the carboxylic acid, amino acid, imine, nitrile, isonitrile, epoxy compound, amine, β-dicarbonyl compound, silane, And by dispersing silica fine particles in water and / or an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of metal compounds having functional groups. Silica fine particles having a reactive functional group a on the surface.
When the reactive silica fine particles (A) of (i) are used, there is an advantage that the film strength can be improved even if the organic component content is small.

  The surface modifying compound used in the reactive silica fine particles (A) of (i) is a carboxyl group, an acid anhydride group, an acid chloride group, an acid amide group, an ester group, an imino group, a nitrile group, an isonitrile group, Hydroxyl group, thiol group, epoxy group, primary, secondary and tertiary amino group, Si—OH group, hydrolyzable residue of silane, C—H acid group such as β-dicarbonyl compound, etc. And having a functional group capable of chemically bonding with a group present on the surface of the silica fine particle under dispersion conditions. The chemical bond here preferably includes a covalent bond, an ionic bond or a coordinate bond, but also includes a hydrogen bond. The coordination bond is considered to be complex formation. For example, acidic / base reaction, complex formation or esterification according to Bronsted or Lewis occurs between the functional group of the surface modifying compound and the group on the surface of the silica fine particle. The said surface modification compound used for the reactive silica fine particle (A) of said (i) can be used 1 type or in mixture of 2 or more types.

The surface modifying compound is usually added to the surface modifying compound via the functional group in addition to at least one functional group (hereinafter referred to as the first functional group) that can participate in chemical bonding with the surface group of the silica fine particles. After binding, it has molecular residues that impart new properties to the silica particles. The molecular residue or a part thereof is hydrophobic or hydrophilic and, for example, stabilizes, integrates or activates silica fine particles.
For example, examples of the hydrophobic molecular residue include an alkyl, aryl, alkaryl, aralkyl, or fluorine-containing alkyl group that causes inactivation or repulsion. Examples of the hydrophilic group include a hydroxy group, an alkoxy group, and a polyester group.

  When the molecular residue of the surface modification compound contains a reactive functional group a capable of reacting with the first binder component described later, the first functional group contained in the surface modification compound is the surface of the silica fine particles. It is possible to introduce a reactive functional group a capable of reacting with the first binder component on the surface of the reactive silica fine particles (A) of (i) above. For example, in addition to the first functional group, a surface modification compound further having a polymerizable unsaturated group is preferable.

  On the other hand, the second reactive functional group is contained in the molecular residue of the surface modification compound, and the reactive silica fine particles (A) of (i) are used as a foothold based on the second reactive functional group. The reactive functional group a capable of reacting with the first binder component may be introduced on the surface of For example, a group capable of hydrogen bonding (hydrogen bond forming group) such as a hydroxyl group and an oxy group is introduced as the second reactive functional group, and another hydrogen bond forming group introduced on the surface of the fine particles It is preferable to introduce a reactive functional group a capable of reacting with the first binder component by the reaction of the hydrogen bond forming group of the surface modifying compound. That is, as a surface modification compound, a compound having a hydrogen bond forming group and a compound having a reactive functional group a capable of reacting with a first binder component such as a polymerizable unsaturated group and a compound having a hydrogen bond forming group are used in combination. Is a suitable example. Specific examples of the hydrogen bond-forming group indicate a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, a glycidyl group, an amide group, or an amide bond. Here, the amide bond indicates that the bond unit contains —NHC (O) or> NC (O) —. Among the hydrogen bond forming groups used in the surface modification compound of the present invention, among them, a carboxyl group, a hydroxyl group, and an amide group are preferable.

  The surface modifying compound used in the reactive silica fine particles (A) of (i) above has a molecular weight of 500 or less, more preferably 400 or less, and particularly 200 or less. Since it has such a low molecular weight, it is presumed that the surface of the silica fine particles can be rapidly occupied and aggregation of the silica fine particles can be prevented.

  The surface modification compound used in the reactive silica fine particles (A) of (i) is preferably a liquid under the reaction conditions for surface modification, and is soluble or at least emulsifiable in a dispersion medium. preferable. Among these, it is preferable that the polymer is dissolved in the dispersion medium and uniformly distributed as discrete molecules or molecular ions in the dispersion medium.

  Saturated or unsaturated carboxylic acids have 1 to 24 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, Examples include adipic acid, succinic acid, glutaric acid, oxalic acid, maleic acid, fumaric acid, itaconic acid and stearic acid, and the corresponding acid anhydrides, chlorides, esters and amides such as caprolactam. Further, when an unsaturated carboxylic acid is used, a polymerizable unsaturated group can be introduced.

Examples of preferred amines are those having the chemical formula Q _3-n NH _n (n = 0, 1 or 2), wherein the residue Q is independently 1-12, in particular 1-6, particularly preferably 1- Alkyl having 4 carbon atoms (eg, methyl, ethyl, n-propyl, i-propyl and butyl) and aryl, alkaryl or aralkyl having 6-24 carbon atoms (eg, phenyl, naphthyl, tolyl and benzyl) Represents. Examples of preferred amines include polyalkyleneamines, and specific examples are methylamine, dimethylamine, trimethylamine, ethylamine, aniline, N-methylaniline, diphenylamine, triphenylamine, toluidine, ethylenediamine, and diethylenetriamine. .

Preferred β-dicarbonyl compounds are those having 4 to 12, particularly 5 to 8 carbon atoms, such as diketones (such as acetylacetone), 2,3-hexanedione, 3,5-heptanedione, acetoacetic acid, acetoacetate. Examples include acetic acid-C ₁ -C ₄ -alkyl esters (such as acetoacetic acid ethyl ester), diacetyl and acetonylacetone.
Examples of amino acids include β-alanine, glycine, valine, aminocaproic acid, leucine and isoleucine.

  Preferred silanes are hydrolyzable organosilanes having at least one hydrolyzable group or hydroxy group and at least one non-hydrolyzable residue. Here, examples of the hydrolyzable group include a halogen, an alkoxy group, and an acyloxy group. As the non-hydrolyzable residue, a non-hydrolyzable residue having a reactive functional group a and / or not having a reactive functional group a is used. Silanes having at least partially organic residues substituted with fluorine may also be used.

As the silane used is not particularly limited, for _{example, CH 2 = CHSi (OOCCH 3} ) 3, CH 2 = CHSiCl 3, CH 2 = CHSi (OC 2 H 5) 3, CH 2 = CHSi (OC 2 H _{4 OCH 3) 3, CH 2} = CH-CH 2 -Si (OC 2 H 5) 3, CH 2 = CH-CH 2 -Si (OOCCH 3) 3, γ- glycidyloxypropyltrimethoxysilane (GPTS), γ-glycidyloxypropyldimethylchlorosilane, 3-aminopropyltrimethoxysilane (APTS), 3-aminopropyltriethoxysilane (APTES), N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- [ N '-(2'-aminoethyl) -2-aminoethyl] -3-aminopropyltrimethoxy Sisilane, hydroxymethyltrimethoxysilane, 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane, bis- (hydroxyethyl) -3-aminopropyltriethoxysilane, N-hydroxyethyl-N-methylaminopropyltriethoxysilane , 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and the like.

  The silane coupling agent is not particularly limited, and may include known ones. For example, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 (trade names, both And Shin-Etsu Chemical Co., Ltd.).

As a metal compound which has a functional group, the metal compound of the metal M from 1st group III-V and / or 2nd group II-IV of an element periodic table is mentioned. Zirconium and titanium alkoxides, M (OR) ₄ (M = Ti, Zr), wherein part of the OR group is replaced by a complexing agent such as a β-dicarbonyl compound or a monocarboxylic acid. Can be mentioned. When a compound having a polymerizable unsaturated group (such as methacrylic acid) is used as a complexing agent, a polymerizable unsaturated group can be introduced.

As the dispersion medium, water and / or an organic solvent is preferably used. A particularly preferred dispersion medium is distilled (pure) water. As the organic solvent, polar, nonpolar and aprotic solvents are preferred. Examples thereof include alcohols such as aliphatic alcohols having 1 to 6 carbon atoms (especially methanol, ethanol, n (normal)-and i (iso) -propanol and butanol), methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, acetone and Ketones such as butanone, esters such as ethyl acetate; ethers such as diethyl ether, tetrahydrofuran and tetrahydropyran; amides such as dimethylacetamide and dimethylformamide; sulfoxides and sulfones such as sulfolane and dimethyl sulfoxide; and pentane; Aliphatic (optionally halogenated) hydrocarbons such as hexane and cyclohexane. These dispersion media can be used as a mixture.
The dispersion medium preferably has a boiling point that can be easily removed by distillation (optionally under reduced pressure), and a solvent having a boiling point of 200 ° C. or lower, particularly 150 ° C. or lower is preferable.

  In the preparation of the reactive silica fine particles (A) of (i), the concentration of the dispersion medium is usually 40% by weight to 90% by weight, preferably 50% by weight to 80% by weight, particularly 55% by weight to 75% by weight. . The remainder of the dispersion is composed of untreated silica fine particles and the surface modifying compound. Here, the weight ratio of silica fine particles / surface modification compound is preferably 100: 1 to 4: 1, more preferably 50: 1 to 8: 1, and further preferably 25: 1 to 10: 1. .

  The preparation of the reactive silica fine particles (A) of (i) is preferably performed at room temperature (about 20 ° C.) to the boiling point of the dispersion medium. Particularly preferably, the dispersion temperature is 50 ° C to 100 ° C. The dispersion time depends in particular on the type of material used, but is generally from a few minutes to a few hours, for example from 1 to 24 hours.

(Ii) a reactive functional group a introduced into the silica fine particles before coating, a compound represented by the following chemical formula (1), a compound containing a silanol group or a group that generates a silanol group by hydrolysis, and silica fine particles as a core Silica fine particles having a reactive functional group a on the surface, obtained by bonding the metal oxide fine particles.
Chemical formula (1)
−Q ¹ −C (= Q ² ) −Q ³ −
In chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), Q ² represents O or S, and Q ³ represents NH or a divalent or higher valent organic group. .
When the reactive silica fine particles (A) of (ii) are used, there are advantages that the amount of organic components is increased, and dispersibility and film strength are further increased.

First, a compound containing a reactive functional group a to be introduced into silica fine particles before coating, a group represented by the above chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis (hereinafter referred to as reactive functional group-modified hydrolysis). The case may be referred to as decomposable silane).
In the reactive functional group-modified hydrolyzable silane, the reactive functional group a desired to be introduced into the silica fine particles is not particularly limited as long as it is appropriately selected so that it can react with a first binder component described later. Suitable for introducing polymerizable unsaturated groups as described above.

In the reactive functional group-modified hydrolyzable silane, the [—Q ¹ —C (═Q ² ) —] moiety of the group represented by the chemical formula (1) is specifically [—O—C (═O )-], [-OC (= S)-], [-SC (= O)-], [-NH-C (= O)-], [-NH-C (= S)- ] And [-S-C (= S)-]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, at least of a [—O—C (═O) —] group, a [—O—C (═S) —] group, and a [—S—C (═O) —] group. It is preferable to use one type in combination. The group [—Q ¹ —C (= Q ² ) —Q ³ —] represented by the chemical formula (1) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength when formed into a cured product. It is considered that properties such as adhesion to the substrate and heat resistance can be imparted.

  Examples of the group that generates a silanol group by hydrolysis include groups having an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, etc. on the silicon atom. An oxysilyl group is preferred. A silanol group or a group that forms a silanol group by hydrolysis can be combined with the metal oxide fine particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

  Specific examples of the reactive functional group-modified hydrolyzable silane include compounds represented by the following chemical formulas (2) and (3). The compound represented by the chemical formula (3) is more preferable in terms of hardness. Preferably used.

In the chemical formulas (2) and (3), R ^a and R ^b may be the same or different, and are a hydrogen atom or a C ₁ to C ₈ alkyl group or aryl group, for example, methyl, ethyl, propyl, Examples thereof include butyl, octyl, phenyl and xylyl groups. Here, m is 1, 2 or 3.
Examples of the group represented by [(R ^a O) _m R ^b _3-m Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

In the chemical formulas (2) and (3), R ^c is a divalent organic group having a C ₁ to C ₁₂ aliphatic or aromatic structure, and may contain a chain, branched or cyclic structure. . Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, phenylene and the like.

In the chemical formula (2), R ^d is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. In addition, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the chemical formula (1). It can also be included.

In the chemical formulas (2) and (3), R ^e is an (n + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

  In the chemical formulas (2) and (3), Y ′ represents a monovalent organic group having a reactive functional group a. The reactive functional group a itself as described above may be used. For example, when the reactive functional group a is selected from a polymerizable unsaturated group, a (meth) acryloyl (oxy) group, a vinyl (oxy) group, a propenyl (oxy) group, a butadienyl (oxy) group, a styryl (oxy) group Ethynyl (oxy) group, cinnamoyl (oxy) group, maleate group, (meth) acrylamide group and the like. N is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.

  For the synthesis of the reactive functional group-modified hydrolyzable silane used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, for example, when it is desired to introduce a polymerizable unsaturated group, (i) it is carried out by an addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound capable of reacting with an isocyanate group. it can. Further, (b) the reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen group-containing polymerizable unsaturated compound. Furthermore, (c) it can also be directly synthesized by an addition reaction of a compound having a polymerizable unsaturated group and an isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

  In the production of the reactive silica fine particles (A) of (ii), a method of separately hydrolyzing the reactive functional group-modified hydrolyzable silane, and then mixing this with the silica fine particles, followed by heating and stirring operations Or a method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of silica fine particles, and other components such as polyunsaturated organic compounds, monounsaturated organic compounds, radiation polymerization initiators, etc. A method of performing surface treatment of the silica fine particles in the presence of can be selected, but a method of hydrolyzing the reactive functional group-modified hydrolyzable silane in the presence of silica fine particles is preferable. When the reactive silica fine particles (A) (ii) are produced, the temperature is usually 20 ° C. or higher and 150 ° C. or lower, and the treatment time is in the range of 5 minutes to 24 hours.

  In order to accelerate the hydrolysis reaction, an acid, salt or base may be added as a catalyst. Suitable acids include organic acids and unsaturated organic acids; examples of bases include tertiary amines or quaternary ammonium hydroxides. The amount of the acid or base catalyst added is 0.001% to 1.0% by weight, preferably 0.01% to 0.1% by weight, based on the reactive functional group-modified hydrolyzable silane.

  As the reactive silica fine particles (A), powdery fine particles not containing a dispersion medium may be used. However, it is possible to omit the dispersion step and to use fine particles as a solvent dispersion sol from the viewpoint of high productivity. preferable.

  As a commercial item of the reactive silica fine particles (A), MIBK-SD, MIBK-SDMS, MIBK-SDL, MIBK-SDZL, manufactured by Nissan Chemical Industries, Ltd., DP1021, DP1022, manufactured by JGC Catalysts and Chemicals, DP1032, DP1037, DP1041, DP1042, DP1044, V8803-25, etc. can be mentioned.

<Reactive irregular shaped silica fine particles (B)>
Reactive deformed silica fine particles (B) are formed by forming 3 to 20 spherical silica fine particles having an average primary particle diameter of 1 nm to 100 nm by inorganic chemical bonds to form deformed silica fine particles. Have a reactive functional group b.

  The reactive irregularly shaped silica fine particles (B) have a surface area larger than that of the non-aggregated reactive silica fine particles having the same particle size as that of the reactive irregularly shaped silica fine particles (B), so that the adhesiveness to the first binder component is increased. Excellent.

The size of the reactive deformed silica fine particles in which 3 to 20 spherical silica fine particles having an average primary particle size of 1 nm to 100 nm are bonded by an inorganic chemical bond, that is, the average secondary particle size can be appropriately adjusted. It is preferably 5 nm to 300 nm, and more preferably 50 nm to 300 nm.
The size of the reactive irregularly shaped silica fine particles can be measured in the first curable resin composition by the same method as the reactive silica fine particles (A), and the first hard coat layer has a cross section. Observation is made using an SEM photograph or a TEM photograph, and 100 of the observed hardened irregular-shaped silica fine particles are counted and obtained as an average value.

  The reactive irregularly shaped silica fine particles (B) are formed by bonding 3 to 20, preferably 3 to 10 of the fine silica particles by an inorganic chemical bond.

  Examples of the inorganic chemical bond include an ionic bond, a metal bond, a coordination bond, and a covalent bond. Among these, bonds that do not disperse the bonded fine particles even when reactive deformed silica fine particles are added to a polar solvent, specifically, metal bonds, coordinate bonds, and covalent bonds are preferable, and covalent bonds are more preferable. In addition, as a polar solvent, lower alcohols, such as water, methanol, ethanol, and isopropanol, etc. are mentioned, for example.

  The method for producing irregular shaped silica fine particles is not particularly limited as long as the silica fine particles are bonded by an inorganic chemical bond, and a conventionally known method can be appropriately selected and used. For example, it can be obtained by adjusting the concentration or pH of the monodispersed silica fine particle dispersion and performing hydrothermal treatment at a high temperature of 100 ° C. or higher. At this time, a 1st binder component can also be added as needed and the coupling | bonding of a silica fine particle can also be accelerated | stimulated. Further, ions may be removed by passing the silica fine particle dispersion used through an ion exchange resin. Such ion exchange treatment can promote the binding of silica fine particles. After the hydrothermal treatment, the ion exchange treatment may be performed again.

  As the reactive functional group b of the reactive irregularly shaped silica fine particles (B), a polymerizable unsaturated group is preferably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. is there. Specific examples thereof include ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group.

The method of introducing the reactive functional group b on the surface of the irregular silica fine particle to obtain the reactive irregular silica fine particle (B) is a method of introducing the reactive functional group a into the silica fine particle of the reactive silica fine particle (A). Can be used.
The reactive functional group a of the reactive silica fine particles (A) and the reactive functional group b of the reactive irregularly shaped silica fine particles (B) may be the same or different.

  As a commercial item of the said reactive unusual shape silica fine particle (B), DP1039, DP1040, DP1071, DP1072, DP1073, V8803-25 etc. by JGC Catalysts and Chemicals Co., Ltd. can be mentioned.

(2) 1st binder component The 1st binder component contained in a 1st curable resin composition is a component used as the matrix of a 1st hard-coat layer. The first binder component usually has a reactive functional group. As the reactive functional group, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group.

  The first binder component is preferably a curable organic resin, preferably a translucent material that transmits light when formed into a coating film, and an ionizing radiation cured resin that is cured by ionizing radiation represented by ultraviolet rays or electron beams. A suitable resin or other known curable resin may be employed depending on the required performance. Examples of the ionizing radiation curable resin include acrylate-based, oxetane-based, and silicone-based resins. The first binder component is preferably at least one of a monomer, an oligomer and a prepolymer. As the first binder component, one or more first binder components can be used.

  It is preferable that the ratio of the 1st binder component in a 1st hard-coat layer exists in the range of 3 weight%-60 weight%, for example.

  The first binder component preferably has three or more reactive functional groups from the viewpoint of increasing the crosslinking density.

Examples of the first binder component having three or more reactive functional groups (three or more functional groups) include, for example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Examples include pentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane hexa (meth) acrylate, and modified products thereof.
Examples of modified products include EO (ethylene oxide) modified products, PO (propylene oxide) modified products, CL (caprolactone) modified products, and isocyanuric acid modified products.

  In addition, a compound having a skeleton similar to the compound (E) having two or more reactive functional groups and a molecular weight of less than 10,000, which will be described later, and having a molecular weight of 10,000 or more and three or more functional groups may be used. it can. Examples of such a compound include trade name beam set 371 manufactured by Arakawa Chemical Industries, Ltd.

  As the first binder component, pentaerythritol triacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, and dipentaerythritol pentaacrylate are preferably used. Dipentaerythritol hexaacrylate, pentaerythritol Tetraacrylate and dipentaerythritol pentaacrylate are particularly preferably used.

  In addition, from the viewpoint of improving hardness in the first hard coat layer, as the first binder component, a polyalkylene oxide chain-containing polymer (D) represented by the following chemical formula (4) and two or more reactive functional groups It is preferable to use in combination with a compound (E) having a molecular weight of less than 10,000.

In the chemical formula (4), X is a linear, branched, or cyclic hydrocarbon chain, either alone or in combination. The hydrocarbon chain may have a substituent, and between the hydrocarbon chains. Is a trivalent or higher valent organic group having 3 to 10 carbon atoms, excluding the above substituents, which may contain different atoms. k represents an integer of 3 to 10. L _{1 to} L _k are each independently a divalent group containing one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond, or a direct bond. R _{1 to} R _k are each independently a linear or branched hydrocarbon group having 1 to 4 carbon atoms. n1, n2,... nk are independent numbers. Y _{1 to} Y _k each independently represent a compound residue having one or more reactive functional groups.

(Polyalkylene oxide chain-containing polymer represented by chemical formula (4) (D))
The polyalkylene oxide chain-containing polymer (D) is represented by the following chemical formula (4), and is a polyalkylene oxide chain-containing polymer having a molecular weight of 1000 or more having three or more reactive functional groups at the terminals.

In the chemical formula (4), X is a linear, branched, or cyclic hydrocarbon chain, either alone or in combination. The hydrocarbon chain may have a substituent, and between the hydrocarbon chains. Is a trivalent or higher valent organic group having 3 to 10 carbon atoms, excluding the above substituents, which may contain different atoms. k represents an integer of 3 to 10. L _{1 to} L _k are each independently a divalent group containing one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond, or a direct bond. R _{1 to} R _k are each independently a linear or branched hydrocarbon group having 1 to 4 carbon atoms. n1, n2,... nk are independent numbers. Y _{1 to} Y _k each independently represent a compound residue having one or more reactive functional groups.

In the chemical formula (4), X is a linear, branched, or cyclic hydrocarbon chain, either alone or in combination. The hydrocarbon chain may have a substituent, and between the hydrocarbon chains. Is a trivalent or higher valent organic group having 3 to 10 carbon atoms excluding the above substituents. In the polyalkylene oxide chain-containing polymer (D) represented by the chemical formula (4), X has _k branch points from which the polyalkylene oxide chain (O—R _k ) _nk portion which is a linear side chain appears. Corresponds to the short main chain.

The hydrocarbon chain includes a saturated hydrocarbon such as —CH ₂ — or an unsaturated hydrocarbon such as —CH═CH—. The cyclic hydrocarbon chain may be composed of an alicyclic compound or may be composed of an aromatic compound. Further, different atoms such as O and S may be included between the hydrocarbon chains, and ether bonds, thioether bonds, ester bonds, urethane bonds, and the like may be included between the hydrocarbon chains. In addition, the hydrocarbon chain branched via a different atom with respect to a linear or cyclic hydrocarbon chain is counted as the carbon number of the substituent mentioned later.

  Specific examples of the substituent that the hydrocarbon chain may have include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, a mercapto group, a cyano group, a silyl group, a silanol group, and a nitro group. Group, acetyl group, acetoxy group, sulfone group and the like are mentioned, but not particularly limited. Substituents that may be present in the hydrocarbon chain include hydrocarbon chains that are branched via a hetero atom with respect to a linear or cyclic hydrocarbon chain as described above. A group (RO-, where R is a saturated or unsaturated linear, branched, or cyclic hydrocarbon chain), an alkylthioether group (RS-, where R is a saturated or unsaturated linear chain, A branched or cyclic hydrocarbon chain), an alkyl ester group (RCOO-, where R is a saturated or unsaturated linear, branched, or cyclic hydrocarbon chain). .

X is a trivalent or more organic group having 3 to 10 carbon atoms excluding the substituent. When the number of carbon atoms excluding the above-described substituent of X is less than 3, it is difficult to have three or more polyalkylene oxide chain (O—R _k ) _nk moieties that are linear side chains. On the other hand, when the number of carbon atoms excluding the above substituents of X exceeds 10, the number of flexible parts increases and the hardness of the cured film decreases, which is not preferable. The number of carbon atoms excluding the substituent is preferably 3-7, and more preferably 3-5.

  X is not particularly limited as long as the above conditions are satisfied. For example, what has the following structure is mentioned.

  Among them, preferable structures include the above structures (x-1), (x-2), (x-3), (x-7) and the like.

  Among the raw materials for X, among others, 1,2,3-propanetriol (glycerol), trimethylolpropane, pentaerythritol, dipentaerythritol and the like are polyvalent having 3 to 10 carbon atoms having 3 or more hydroxyl groups in the molecule. Alcohols, polyvalent carboxylic acids having 3 to 10 carbon atoms having 3 or more carboxyl groups in the molecule, polyvalent amine acids having 3 to 10 carbon atoms having 3 or more amino groups in the molecule, etc. Preferably used.

In the chemical formula (4), k represents the number of polyalkylene oxide chains (O—R _k ) _{nk in} the molecule, and represents an integer of 3 to 10. If k is less than 3, that is, if there are two polyalkylene oxide chains, sufficient hardness cannot be obtained. On the other hand, if k exceeds 10, the number of flexible parts increases and the hardness of the cured film decreases, which is not preferable. The k is preferably 3-7, more preferably 3-5.

In the chemical formula (4), L _{1 to} L _k are each independently a divalent group including one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond, or a direct bond. The divalent group containing one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond is an ether bond (—O—), an ester bond (—COO—), a urethane bond (—NHCOO—). ) Itself. Since these bonds are easy to spread molecular chains and have a high degree of freedom, it is easy to achieve compatibility with other resin components.

  Examples of the divalent group containing one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond include —O—R—O— and —O (C═O) —R—O—. -O (C = O) -R- (C = O) O-,-(C = O) O-R-O-,-(C = O) O-R- (C = O) O-, — (C═O) O—R—O (C═O) —, —NHCOO—R—O—, —NHCOO—R—O (C═O) NH—, —O (C═O) NH—R —O—, —O (C═O) NH—R—O (C═O) NH—, —NHCOO—R—O (C═O) NH—, —NHCOO—R— (C═O) O— , —O (C═O) NH—R— (C═O) O—, —NHCOO—R—O (C═O) —, —O (C═O) NH—R—O (C═O) -Etc. are mentioned. Here, R represents a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain.

  Specific examples of the divalent group include, for example, diols such as (poly) ethylene glycol and (poly) propylene glycol, dicarboxylic acids such as fumaric acid, maleic acid, and succinic acid, tolylene diisocyanate, hexamethylene diisocyanate, Although the residue remove | excluding active hydrogen, such as diisocyanates, such as isoboron diisocyanate, is mentioned, It is not limited to these.

In the chemical formula (4), (O—R _k ) _nk is a polyalkylene oxide chain in which alkylene oxide is a linear side chain of a repeating unit. Here, R _{1 to} R _k are each independently a linear or branched hydrocarbon group having 1 to 4 carbon atoms. Examples of the alkylene oxide include methylene oxide, ethylene oxide, propylene oxide, isobutylene oxide, and the like, and ethylene oxide and propylene oxide which are linear or branched hydrocarbon groups having 2 to 3 carbon atoms are preferably used.

N1, n2... Nk, which are the number of repeating units of alkylene oxide R _k —O, are independent numbers. n1, n2,... nk are not particularly limited as long as the weight average molecular weight as a whole molecule is 1000 or more. n1, n2... nk may be different from each other, but it is preferable that the chain lengths are substantially the same from the viewpoint of suppressing cracks while maintaining the hardness when the first hard coat layer is formed. Therefore, the difference between n1, n2,... Nk is preferably about 0 to 100, more preferably about 0 to 50, and particularly preferably about 0 to 10.
From the point of suppressing cracks while maintaining the hardness when the first hard coat layer is formed, n1, n2,... Nk are each preferably 2 to 500, and more preferably 2 to 300. It is preferable.

Y _{1 to} Y _k each independently represent a reactive functional group or a compound residue having one or more reactive functional groups. This results in three or more reactive functional groups at the end of the polyalkylene oxide chain-containing polymer.
When Y _{1 to} Y _k are reactive functional groups themselves, examples of Y _{1 to} Y _k include polymerizable unsaturated groups such as a (meth) acryloyl group and a vinyl group (CH ₂ ═CH—).

Examples of the reactive functional group in the case where Y _{1 to} Y _k are compound residues having one or more reactive functional groups include, for example, (meth) acryloyloxy group, CH ₂ = CR- (where R is A polymerizable unsaturated group such as a hydrocarbon group). When Y _{1 to} Y _k is a compound residue, the number of reactive functional groups that the Y _{1 to} Y _k has may be one, but two or more can further increase the crosslinking density, It is preferable from the point of the hardness at the time of setting it as a 1st hard-coat layer.

When Y _{1 to} Y _k are compound residues having one or more reactive functional groups, the compound residues are further reactive separately from at least one reactive functional group and the reactive functional group. A residue obtained by removing the reactive substituent or a part of the reactive substituent (such as hydrogen) from a compound having a substituent.
For example, as the compound residue having an ethylenically unsaturated group, specifically, for example, a reactive substituent other than the ethylenically unsaturated group of the following compound or a part of the reactive substituent (such as hydrogen) is excluded. Residue. Examples include (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and pentaerythritol tri (meth) acrylate, but are not limited thereto.

  The molecular weight of the polyalkylene oxide chain-containing polymer (D) used in the present invention is 1000 or more, more preferably 5000 or more, and particularly preferably 10,000 from the viewpoint of imparting flexibility to the cured film and preventing cracks. That's it.

Examples of commercially available products containing the polyalkylene oxide chain-containing polymer (D) represented by the chemical formula (4) include, for example, the trade name Diabeam UK-4153 (manufactured by Mitsubishi Rayon; in the chemical formula (4), X is (x -7), k is 3, L _{1 to} L ₃ are each a direct bond, R _{1 to} R ₃ are each ethylene, the total of n1, n2, and n3 is 20, and Y _{1 to} Y ₃ are each an acryloyloxy group. And the like.

  The content of the polymer (D) is preferably 5 to 100 parts by weight and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the compound (E) described later. If the content of the polymer (D) is 5 parts by weight or more with respect to 100 parts by weight of the compound (E) to be described later, the cured film can be given flexibility and restorability, and if it is 100 parts by weight or less, it is cured. The film hardness can be maintained.

(Compound (E) having a molecular weight of less than 10,000 having two or more reactive functional groups)
The compound (E) having two or more reactive functional groups and a molecular weight of less than 10,000 has three or more reactive functional groups contained in one molecule, which increases the crosslinking density of the cured film and increases the hardness. It is preferable from the point which provides. Here, when the compound (E) is an oligomer having a molecular weight distribution, the number of reactive functional groups is represented by an average number.
Moreover, it is preferable that the molecular weight of a compound (E) is less than 5,000 from the point of a hardness improvement.

Specific examples are given below, but the compound (E) used in the present invention is not limited thereto.
As a specific example having a polymerizable unsaturated group, as a polyfunctional (meth) acrylate monomer having two or more polymerizable unsaturated groups in one molecule, for example, 1,6-hexanediol di (meth) acrylate, Bifunctional or reactive functional groups such as neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and isocyanuric acid ethylene oxide-modified di (meth) acrylate; (Meth) acrylate and its EO, PO, epichlorohydrin modified product, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, and its EO, PO, epichlorohydrin modified product, isocyanuric acid EO modified tri (meth) acrylate ( east Synthetic Aronix M-315, etc.), tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate- (2,2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, and its Trifunctional (meth) acrylate compounds such as EO, PO and epichlorohydrin modified products; pentaerythritol tetra (meth) acrylate and tetrafunctional (meth) such as EO, PO, epichlorohydrin modified products and ditrimethylolpropane tetra (meth) acrylate Acrylate compound; Dipentaerythritol penta (meth) acrylate and pentafunctional (meth) acrylate compound such as EO, PO, epichlorohydrin, fatty acid, alkyl, urethane modified product thereof; Dipentaerythritol hexa (meth) acrylate Relate, and its EO, PO, epichlorohydrin, fatty acid, alkyl, urethane modified product, sorbitol hexa (meth) acrylate, and its EO, PO, epichlorohydrin, fatty acid, alkyl, urethane modified product, etc. Can be mentioned.

  Commercially available products can be used as the trifunctional or higher acrylate resin. Specifically, KAYARAD and KAYAMER series (for example, DPHA, PET30, GPO303, TMPTA, THE330, TPA330, manufactured by Nippon Kayaku Co., Ltd.) D310, D330, PM2, PM21, DPCA20, DPCA30, DPCA60, DPCA120); Aronix series manufactured by Toagosei Co., Ltd. (for example, M305, M309, M310, M315, M320, M327, M350, M360, M402, M408, M450, M7100, M7300K, M8030, M8060, M8100, M8530, M8560, M9050); NK ester series (for example, TMPT, A-TMPT, A-TMM-) manufactured by Shin-Nakamura Chemical Co., Ltd. A-TMM3L, A-TMMT, A-TMPT-6EO, A-TMPT-3CL, A-GLY-3E, A-GLY-6E, A-GLY-9E, A-GLY-11E, A-GLY-18E , A-GLY-20E, A-9300, AD-TMP-4CL, AD-TMP); NK Economer series manufactured by Shin-Nakamura Chemical Co., Ltd. (for example, ADP51, ADP33, ADP42, ADP26, ADP15); New Frontier series (for example, TMPT, TMP3, TMP15, TMP2P, TMP3P, PET3, TEICA) manufactured by Ichi Kogyo Seiyaku Co., Ltd .; Ebecryl series (for example, TMPTA, TMPTAN, 160, manufactured by Daicel UCB) TMPEOTA, OTA480, 53, PETIA, 2047, 40, 1 0, 1140, PETAK, DPHA); SARTOMER CD501, CD9021, CD9052, SR351, SR351HP, SR351LV, SR368, SR368D, SR415, SR444, SR454, SR454HP, SR492, SR499, SR502, SR90020, SR9020SR SR9035, CD9051, SR350, SR9009, SE9011, SR295, SR355, SR399, SR399LV, SR494, SR9041 and the like.

  Examples of (meth) acrylate oligomers (or prepolymers) include epoxy (meth) acrylates obtained by addition reaction of glycidyl ether and a monomer having (meth) acrylic acid or a carboxylate group; polyols and polyisocyanates; (Meth) acrylates obtained by an addition reaction between a reaction product of (1) and a hydroxyl group-containing (meth) acrylate; polyesters obtained by esterification of a polyester polyol comprising a polyol and a polybasic acid and (meth) acrylic acid Examples of acrylates include polybutadiene (meth) acrylate, which is a (meth) acrylic compound having a polybutadiene or hydrogenated polybutadiene skeleton. When the reactive functional group which the essential component in this invention has is a polymerizable unsaturated group, especially urethane (meth) acrylate is used suitably from the point which gives hardness and a softness | flexibility to a cured film.

Examples of the glycidyl ether used in the epoxy (meth) acrylates include 1,6-hexane diglycidyl ether, polyethylene glycol glycidyl ether, bisphenol A type epoxy resin, naphthalene type epoxy resin, cardo epoxy resin, and glycerol triglycidyl ether. And phenol novolac type epoxy resins.
Examples of the polyol used in the urethane (meth) acrylates include 1,6-hexane diglycidyl ether, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone diol, polycarbonate diol, polybutadiene polyol, and polyester diol. Etc. Examples of the polyisocyanate used in the urethane (meth) acrylates include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, hexamelletin diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and the like. Examples of the (meth) acrylate containing a hydroxyl group used in the urethane (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and pentaerythritol. (Meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate and the like.
Examples of the polyol for forming the polyester polyol used in the polyester acrylates include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, 1,4-butanediol, trimethylolpropane, and pentaerythritol. Examples of the polybasic acid include succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid.

  Moreover, as a compound (E) used for this invention, the polymer represented by following Chemical formula (5) whose molecular weight is less than 10,000 can also be used.

  In chemical formula (5), D represents a linking group having 1 to 10 carbon atoms, and q represents 0 or 1. R represents a hydrogen atom or a methyl group. E represents a polymerization unit of an arbitrary vinyl monomer, and may be composed of a single component or a plurality of components. o and p are mol% of each polymerized unit. p may be 0.

  D in the chemical formula (5) represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, which is linear. May have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.

Preferred examples of the linking group D in the chemical formula (5) include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O. _{- **, * - (CH 2} ) 6 -O - **, * - (CH 2) 2 -O- (CH) 2 -O - **, * - CONH- (CH 2) 3 -O- * *, * —CH ₂ CH (OH) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** and the like. Here, * represents a connecting site on the polymer main chain side, and ** represents a connecting site on the (meth) acryloyl group side.

  In chemical formula (5), R represents a hydrogen atom or a methyl group, and is more preferably a hydrogen atom from the viewpoint of curing reactivity.

  In the chemical formula (5), o may be 100 mol%, that is, a single polymer. Moreover, even if o is 100 mol%, the copolymer in which 2 or more types of polymerization units containing the (meth) acryloyl group represented by o mol% were used may be used. The ratio of o and p is not particularly limited and can be appropriately selected from various viewpoints such as hardness, solubility in a solvent, and transparency.

  In chemical formula (5), E represents a polymerized unit of an arbitrary vinyl monomer, and is not particularly limited, and can be appropriately selected from various viewpoints such as hardness, solubility in a solvent, and transparency. You may be comprised by the single or several vinyl monomer.

  For example, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, allyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, etc. (Meth) acrylates such as vinyl esters, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane, Styrene derivatives such as styrene and p-hydroxymethyl styrene, and unsaturated hydrocarbons such as crotonic acid, maleic acid and itaconic acid. Mention may be made of carbon acid and derivatives thereof.

  Moreover, the reactive oligomer which has an ethylenically unsaturated bond in the terminal and side chain whose weight average molecular weight is less than 10,000 can also be used. As the reactive oligomer, the skeleton component is poly (meth) acrylate methyl, polystyrene, poly (meth) butyl acrylate, poly (acrylonitrile / styrene), poly ((meth) acrylate 2-hydroxymethyl / (meth) Methyl acrylate), poly (2-hydroxymethyl (meth) acrylate / butyl (meth) acrylate), and copolymers of these resins and silicone resins.

  Commercially available products can be used for the above compounds. As urethane acrylate having a weight average molecular weight of less than 10,000 and having two or more polymerizable unsaturated groups, Kyoeisha Chemical Co., Ltd. trade names AH-600, AT-600, UA-306H, UA-306T, UA-306I etc. are mentioned. As a urethane (meth) acrylate suitably used in combination with the polymer (D) of the present invention, a monomer or multimer of isophorone diisocyanate, a pentaerythritol polyfunctional acrylate, and a dipentaerythritol polyfunctional acrylate are reacted. The urethane (meth) acrylate obtained is mentioned. As a commercial item of the said urethane (meth) acrylate, brand name UV-1700B (made by Nippon Synthetic Chemical Industry Co., Ltd.) is mentioned, for example.

  A commercially available product can be used as the urethane (meth) acrylate resin, and specific examples include the purple light series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., such as UV1700B, UV6300B, UV765B, UV7640B, and UV7600B; Art Resin series manufactured by Kogyo Co., Ltd., for example, Art Resin HDP, Art Resin UN 9000H, Art Resin UN 3320HA, Art Resin UN 3320HB, Art Resin UN 3320HC, Art Resin UN 3320HS, Art Resin UN901M, Art Resin UN902MS, Art Resin UN903, etc. And UA100H, U4H, U6H, U15HA, UA32P, U6LPA, U324A, U9HAMI, etc. manufactured by Shin-Nakamura Chemical Co., Ltd .; Ebecryl series manufactured by, for example, 1290, 5129, 254, 264, 265, 1259, 1264, 4866, 9260, 8210, 204, 205, 6602, 220, 4450, etc .; Arakawa Chemical Industries, Ltd. Beamset series manufactured by, for example, 777, 577BV, 777AK, etc .; RQ series manufactured by Mitsubishi Rayon Co., Ltd .; unidic series manufactured by DIC Corporation, etc .; DPHA40H (Nippon Kayaku) CN9006, CN968 (made by SARTOMER), etc. are mentioned. Of these, UV1700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), DPHA40H (manufactured by Nippon Kayaku Co., Ltd.), Art Resin HDP (manufactured by Negami Industrial Co., Ltd.), Beam Set 577 (Arakawa Chemical Industries, Ltd.) )), U15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

  Moreover, as an epoxy acrylate having a weight average molecular weight of less than 10,000 and having two or more polymerizable unsaturated groups, trade name SP series (SP-4060, 1450, etc.), VR series, manufactured by Showa Polymer Co., Ltd. (VR-60, 1950; VR-90, 1100, etc.), etc .; Nippon Synthetic Chemical Industry Co., Ltd., trade name UV-9100B, UV-9170B, etc .; Shin-Nakamura Chemical Co., Ltd., trade name EA-6320 / PGMAc EA-6340 / PGMAc and the like.

  Moreover, as a reactive oligomer having a weight average molecular weight of less than 10,000 and having two or more polymerizable unsaturated groups, trade name Macromonomer Series AA-6, AS-6, AB- manufactured by Toagosei Co., Ltd. 6, AA-714SK and the like.

In consideration of the curling property and cracking property of the first hard coat layer, those having the same repeating unit as in the chemical formula (5) and having a molecular weight of 10,000 or more and less than 100,000 may be added as the first binder component.
Examples of the first binder component having a molecular weight of 10,000 or more and less than 100,000 include BS371, BS371MLV, DK1, DK2, and DK3 manufactured by Arakawa Chemical Industries, Ltd.

(3) First surfactant The first surfactant contained in the first curable resin composition is a component that imparts antifouling properties to the first hard coat layer. Here, “giving antifouling property” means changing the contact angle of water droplets in the first hard coat layer to 90 ° or more by adding the first surfactant. Moreover, as a 1st surfactant, Si-F type surfactant etc. can be mentioned, for example. Specific examples include X-71-1203M (manufactured by Shin-Etsu Chemical Co., Ltd., Si—F surfactant). Further, the ratio of the first surfactant in the first hard coat layer is preferably, for example, 0.5% by weight or less, and more preferably 0.2% by weight or less.

(4) Polymerization initiator The first curable resin composition preferably contains a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radicals and cationic polymerization initiators.

Any radical polymerization initiator may be used as long as it can release a substance that initiates radical polymerization by light irradiation and / or heating. For example, examples of the photo radical polymerization initiator include imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocenes, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like. More specifically, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5- Isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name Irgacure 651, Ciba Japan Co., Ltd.) 1-hydroxy-cyclohexyl-phenyl- T (trade name Irgacure 184, manufactured by Ciba Japan Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade names Irgacure 369, Ciba Japan ( Co., Ltd.), bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium) (trade name Irgacure 784, manufactured by Ciba Japan Co., Ltd.), etc., but is not limited thereto.

  In addition to the above, commercially available products can be used. Specifically, Irgacure 907, Irgacure 184, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800 manufactured by Ciba Japan Co., Ltd. , Irgacure 1870, Irgacure OXE01, DAROCUR TPO, DAROCUR 1173, Nippon Shibel Hegner's YDE SPEEDCure EMB, SpeedCurEB, SpeedKurEp , KAYACURE CTX, KAYA URE BMS, KAYACURE DMBI, and the like.

Moreover, the cationic polymerization initiator should just be able to discharge | release the substance which starts cationic polymerization by light irradiation and / or a heating. Examples of the cationic polymerization initiator include sulfonic acid ester, imide sulfonate, dialkyl-4-hydroxysulfonium salt, arylsulfonic acid-p-nitrobenzyl ester, silanol-aluminum complex, (η ⁶ -benzene) (η ⁵ -cyclopentadidiene). Enyl) iron (II) and the like are exemplified, and more specifically, benzoin tosylate, 2,5-dinitrobenzyl tosylate, N-tosiphthalimide and the like are exemplified, but not limited thereto.

  Examples of radical polymerization initiators that can be used as cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron arene complexes, and the like. More specifically, iodonium chloride such as diphenyliodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoro Iodonium salts such as antimonate salts, chlorides of sulfonium such as triphenylsulfonium, 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, bromides, borofluorides, hexaf Sulfonium salts such as orophosphate salts and hexafluoroantimonate salts, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1, 2,4,6-substituted-1,3,5 triazine compounds such as 3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, etc. It is not limited to these.

(5) Other components The first curable resin composition usually contains a solvent. Although the kind of solvent is not specifically limited, For example, methyl isobutyl ketone, propylene glycol monomethyl ether, normal propanol, isopropanol, normal butanol, sec-butanol, isobutanol, tert-butanol etc. are mentioned. Furthermore, the first curable resin composition may contain an antistatic agent, an antiglare agent, a leveling agent, various sensitizers, and the like as necessary.

(6) 1st hard-coat layer Although the thickness of the 1st hard-coat layer in this invention is not specifically limited, For example, it is preferable to exist in the range of 5 micrometers-20 micrometers. This is because if the first hard coat layer is too thin, sufficient scratch resistance cannot be exhibited, and if the first hard coat layer is too thick, it causes warping and cracks.

  The first hard coat layer is formed on one surface side of the transparent resin plate, and may be directly formed on the transparent resin plate, or may be formed on the transparent resin plate via another layer. May be. Examples of other layers include a primer layer, an antistatic layer, an antiglare layer, and a low refractive index layer. The first hard coat layer is formed by curing the first curable resin composition described above. Since the method for forming the first hard coat layer will be described later, description thereof is omitted here.

2. Second Hard Coat Layer The second hard coat layer in the present invention has a polymer containing a second binder component and a second surfactant imparting printability. For example, when the second hard coat layer has reactive silica fine particles, the reactive functional groups of the reactive silica fine particles and the reactive functional groups of the second binder component are respectively between the same or different reactive functional groups. A polymer is formed by crosslinking. Further, the second surfactant may be a component of the polymer, that is, may be crosslinked with reactive silica fine particles or the like, or may be dispersed around the polymer.

  The second hard coat layer in the present invention is a layer that imparts a hardness higher than the hardness on the surface before the second hard coat layer is formed. The hardness of the second hard coat layer can be evaluated by the pencil hardness test described above. The pencil hardness of the second hard coat layer is preferably 3H or more, for example. This is because the impact resistance is improved. On the other hand, the pencil hardness of the second hard coat layer is preferably 9H or less, for example. This is because if the pencil hardness is too high, brittleness increases, causing warping and cracking.

  In the second hard coat layer in the present invention, the contact angle of water droplets is preferably 80 ° or less, more preferably 70 ° or less, and further preferably 60 ° or less. This is because good printability can be exhibited. On the other hand, the contact angle of the water droplet is preferably 40 ° or more. This is because if the contact angle is too small, the wettability becomes too high, and conversely the printability becomes low.

  Moreover, a 2nd hard-coat layer is normally comprised from the hardened | cured material of the 2nd curable resin composition containing a 2nd binder component and a 2nd surfactant. In addition, the 2nd curable resin composition may contain the reactive silica fine particle, and does not need to contain it. In the former case, there is an advantage that the hardness of the second hard coat layer is increased and impact resistance is improved. In the latter case, there is an advantage that the followability of the second hard coat layer can be kept high and the occurrence of cracks can be suppressed.

(1) Reactive silica fine particles The reactive silica fine particles contained in the second curable resin composition are the same as those described above for the reactive silica fine particles contained in the first curable resin composition. Moreover, the reactive silica fine particles contained in the second curable resin composition may be the same material as the reactive silica fine particles contained in the first curable resin composition, or may be a different material. The same material is preferred. This is because warpage can be further suppressed. The ratio of the reactive silica fine particles in the second hard coat layer is preferably in the range of 20 wt% to 80 wt%, for example, and more preferably in the range of 40 wt% to 60 wt%.

(2) Second Binder Component The second binder component contained in the second curable resin composition is the same as that described above for the first binder component contained in the first curable resin composition. The second binder component may be the same type as the first binder component, for example, acrylic monomers, or different types, but the same type is preferable. Further, the second binder component may be the same material as the first binder component or a different material, but is preferably the same material. This is because warpage can be further suppressed. That is, when the second binder component and the first binder component are the same type or the same material, the first hard coat layer exhibits antifouling properties depending on the material other than the binder component, for example, the type of surfactant. And causing the second hard coat layer to exhibit printability. Therefore, the followability of the first hard coat layer and the second hard coat layer is basically the same, and the occurrence of warpage can be further suppressed. The ratio of the second binder component in the second hard coat layer is preferably in the range of 3 wt% to 60 wt%, for example.

(3) Second surfactant The second surfactant contained in the second curable resin composition is a component that imparts printability to the second hard coat layer. Here, “giving printability” means changing the contact angle of water droplets in the second hard coat layer within the range of 40 ° to 80 ° by the addition of the second surfactant. Moreover, as a 2nd surfactant, Si-F type surfactant etc. can be mentioned, for example. Specific examples include TF1682 (manufactured by DIC, Si-F surfactant). Further, the ratio of the second surfactant in the second hard coat layer is, for example, preferably 0.5% by weight or less, and more preferably 0.2% by weight or less.

(4) Polymerization initiator and other components The polymerization initiator and other components contained in the second curable resin composition are the same as in the case of the first curable resin composition described above. The description in is omitted.

(5) Second Hard Coat Layer The thickness of the second hard coat layer in the present invention is not particularly limited. Moreover, the preferable range of thickness is the same as the case in the 1st hard-coat layer mentioned above. The thickness of the second hard coat layer may be substantially the same as or different from the thickness of the first hard coat layer. Note that “substantially the same” means that the difference in thickness (strictly, average thickness) between the second hard coat layer and the first hard coat layer is 3 μm or less.

  The second hard coat layer is formed on one surface side of the transparent resin plate, may be directly formed on the transparent resin plate, and is formed on the transparent resin plate via the other layer. May be. Examples of other layers include a primer layer, an antistatic layer, an antiglare layer, and a low refractive index layer. The second hard coat layer is obtained by curing the second curable resin composition described above. Since the method for forming the second hard coat layer will be described later, description thereof is omitted here.

  Moreover, in this invention, it is preferable that the thermal expansion coefficient and hygroscopic expansion coefficient of a 2nd hard-coat layer and a 1st hard-coat layer are near. This is because warpage can be further suppressed.

3. Transparent resin board The transparent resin board in this invention is a resin board which has transparency (light transmittance), and if it satisfy | fills the physical property which can be used as a transparent base material of an optical laminated body, it will not specifically limit. Usually, the transparent base material used for the optical layered body may be transparent, translucent, colorless, or colored, but is required to have light transmittance.

  Examples of the material for the transparent resin plate include acrylate polymers, polycarbonates, polyesters, cellulose acylates, and cycloolefin polymers. Specific examples of the acrylate polymer include methyl poly (meth) acrylate, poly (meth) ethyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate, and the like. Specific examples of the polycarbonate include aromatic polycarbonates based on bisphenols (such as bisphenol A) and aliphatic polycarbonates such as diethylene glycol bisallyl carbonate. Specific examples of the polyester include polyethylene terephthalate and polyethylene naphthalate. Specific examples of cellulose acylate include cellulose triacetate, cellulose diacetate, and cellulose acetate butyrate. Specific examples of the cycloolefin polymer include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymer resins, and the like.

  The transparent resin plate may have a single layer structure or a multilayer structure. In the former case, the material of the transparent resin plate is preferably an acrylate polymer, more preferably polymethyl methacrylate (PMMA), and high transparency. On the other hand, in the latter case, the transparent resin plate has a plurality of transparent resin layers. The number of the plurality of transparent resin layers may be two or more, preferably in the range of 3 to 5, and more preferably 3.

  When the transparent resin plate has three or more transparent resin layers, the two outermost layers are the outermost transparent resin layers, and the layers located inside the two outermost transparent resin layers are the inner transparent resin layers. . As shown in FIG. 2, for example, when the transparent resin plate 1 is composed of three transparent resin layers, the two outermost layers are the outermost transparent resin layers 1b and the two outermost transparent resin layers 1b. The layer located inside is referred to as an inner transparent resin layer 1a. The inner transparent resin layer 1a may be a multilayer.

  When the transparent resin plate has three or more transparent resin layers, the pencil hardness of the two outermost transparent resin layers is preferably higher than the pencil hardness of the inner transparent resin layer. By increasing the hardness of the outermost transparent resin layer, it becomes easy to form a hard coat layer with high hardness, and by reducing the hardness of the inner transparent resin layer, stress caused by differences in thermal expansion coefficient, etc. can be relaxed, That is, the inner transparent resin layer becomes a cushion layer, and impact resistance (eg, falling ball resistance) is improved. The difference in hardness between the outermost transparent resin layer and the inner transparent resin layer is preferably separated by two or more steps, more preferably by three or more steps, on the basis of pencil hardness. For example, the pencil hardness of the outermost transparent resin layer is preferably HB or higher, and more preferably H or higher and 5H or lower. The pencil hardness of the inner transparent resin layer is preferably H or less, for example, and more preferably 3B or more and HB or less. When the transparent resin plate has a single layer structure, the pencil hardness of the transparent resin plate is preferably 3B or more and 5H or less, for example.

  In the present invention, as shown in FIG. 2, the transparent resin plate 1 is composed of three transparent resin layers, the inner transparent resin layer 1a is polycarbonate, and the two outermost transparent resin layers 1b are acrylate-based. A polymer is preferred. This is because impact resistance (for example, drop ball resistance) is improved. In this case, the thickness of one outermost transparent resin layer is preferably in the range of 70 μm to 100 μm, for example.

  The transparent resin plate preferably transmits more light. For example, the transmittance in the visible light region is preferably 80% or more, and more preferably 90% or more. In addition, let the light transmittance of a transparent resin board be the value (total light transmittance) measured by the method prescribed | regulated by JISK7105.

  Although the thickness of a transparent resin board is not specifically limited, It is preferable that it is 0.3 mm or more, and it is more preferable that it exists in the range of 0.3 mm-5 mm. This is because, within the above range, it is possible to prevent an increase in the size of the protective body, that is, an increase in the thickness of the protective body while maintaining sufficient impact resistance. The transparent resin plate may be subjected to a surface treatment (for example, saponification treatment, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, flame treatment).

4). Protective body The total thickness of the protective body varies depending on the layer structure and the like, and is not particularly limited. However, it is preferably within a range of 0.3 mm to 5 mm, for example. This is because, within the above range, it is possible to prevent an increase in the size of the protective body, that is, an increase in the thickness of the protective body, while maintaining a sufficient impact resistance. Further, the use of the protector of the present invention is not particularly limited. For example, the contact-type image display device such as a touch panel, non-contact such as a liquid crystal display, a CRT display, a projection display, a plasma display, and an electroluminescence display. Application of a solar cell such as a dye-sensitized solar cell and the like. Especially, it is preferable that the protector of this invention is used as a front plate of a touch panel. This is because the front plate of the touch panel is a member that comes into direct contact with the finger, and high scratch resistance and antifouling properties are required. In addition, with the spread of touch panels, improvement in design properties is required, and high printability is required.

5. The manufacturing method of a protector The manufacturing method of the protector of this invention will not be specifically limited if it is a method which can obtain the protector mentioned above. FIG. 3 is a schematic cross-sectional view showing an example of a method for producing a protector according to the present invention. In FIG. 3, first, a transparent resin plate 1 is prepared (FIG. 3A). Then, the 1st curable resin composition is apply | coated to one surface side of the transparent resin board 1, a coating film is formed, it dries, Then, a coating film is hardened with light, The 1st hard-coat layer 2a (FIG. 3B). Thereafter, the second curable resin composition is applied to the other surface side of the transparent resin plate 1, a coating film is formed, drying is performed, and then the coating film is cured by at least one of light and heat. 2 Hard coat layer 2b is formed (FIG. 3C).

The curable resin composition is prepared by mixing and dispersing raw materials. A paint shaker or a bead mill can be used for mixing and dispersing. The coating method is not particularly limited, and spin coating method, dip method, spray method, slide coating method, bar coating method, roll coater method, meniscus coater method, flexographic printing method, screen printing method, pea coater method, etc. These various methods can be used. Moreover, it is preferable to adjust as the coating amount of the curable resin composition on a transparent resin board so that the hard-coat layer of a desired film thickness may be obtained. ^{Specifically,} it is preferably in the range of ^{3g / m 2 ~30g / m 2} .

Examples of the drying method include vacuum drying, heat drying, and combinations thereof. When drying at normal pressure, it is preferable to dry in the temperature range in which the transparent resin plate does not deteriorate, for example, in the range of 30 ° C to 110 ° C. Moreover, ultraviolet rays, visible light, an electron beam, ionizing radiation, etc. are mainly used for light irradiation. In the case of ultraviolet curing, ultraviolet rays emitted from light such as an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp are used. The amount of irradiation with the energy radiation source of accumulative exposure at an ultraviolet wavelength of 365 nm, is preferably in the range of, for example, ^{50mJ / cm 2 ~5000mJ / cm 2} . Moreover, when heating, it is preferable to heat in the temperature range with which a transparent resin plate does not deteriorate, for example, it is preferable to heat within the range of 40 to 120 degreeC. Moreover, you may react by leaving it to stand for 24 hours or more at room temperature (25 degreeC). The first hard coat layer and the second hard coat layer may be formed separately or simultaneously.

B. Next, the touch panel module of the present invention will be described. The touch panel module of the present invention includes a touch panel sensor and a protective body formed on the touch panel sensor, and the protective body is the above-described protective body.

  FIG. 4 is a schematic cross-sectional view showing an example of the touch panel module of the present invention. The touch panel module 100 in FIG. 4 includes a touch panel sensor 20 and a protector 10 formed on the touch panel sensor 20. The touch panel sensor 20 includes a transparent substrate 11, a first transparent electrode (for example, an ITO electrode) 12 formed in a pattern on the transparent substrate 11, and an interelectrode insulation formed so as to cover the first transparent electrode 12. A layer (for example, an acrylic resin layer, a cardo resin layer) 13, a second transparent electrode (for example, an ITO electrode) 14 formed in a pattern on the interelectrode insulating layer 13, and a second transparent electrode 14 are formed. And an overcoat layer (for example, an acrylic resin layer, a cardo resin layer) 15 and a decorative layer 16 formed on the overcoat layer 15. Furthermore, the overcoat layer 15 and the decorative layer 16 are disposed so as to be in contact with the second hard coat layer 2b of the protector 10.

  According to the present invention, by using the above-described protector, the occurrence of warpage can be suppressed, and a touch panel module having excellent scratch resistance, antifouling properties, and printability can be obtained.

1. Touch Panel Sensor A general touch panel sensor can be used as the touch panel sensor in the present invention, and the type and layer configuration of each constituent member are not particularly limited. For example, as shown in FIG. 4, the touch panel sensor has a transparent substrate 11, a first transparent electrode 12, an interelectrode insulating layer 13, a second transparent electrode 14, an overcoat layer 15, and a decorative layer 16 in this order. You may do it. Moreover, although not shown in figure, you may use a transparent base material (for example, transparent resin film) as an insulating layer between electrodes. That is, the first transparent electrode may be formed on one surface side of the transparent resin film, and the second transparent electrode may be formed on the other surface side of the transparent resin film. Further, the second transparent electrode may be formed on the surface of the second hard coat layer without the overcoat layer 15 being interposed.

  Moreover, it is preferable that the touch panel sensor in this invention has a decoration layer in the surface which contact | connects the 2nd hard-coat layer of a protector. It is because it can be set as a highly design touch panel sensor. In addition, a decoration layer means the layer for improving the designability, for example, is a layer which has a concealment function. Specifically, the layer colored black or white is mentioned. Moreover, the decoration layer may be formed in the peripheral area | region which does not overlap with the sensor part of a touchscreen sensor in planar view, and may be formed in the center area | region which overlaps with the sensor part of a touchscreen sensor. A decoration layer is a layer containing a coloring agent, a binder, and a dispersing agent, for example. The decorative layer can be formed by, for example, a screen printing method, a photolithography method, or an ink jet method.

2. Protective Body Since the protective body in the present invention is the same as the contents described in the above-mentioned “A. Protective body”, description thereof is omitted here.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the technical idea described in the claims of the present invention has substantially the same configuration and exhibits the same function and effect regardless of the case. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Example 1]
(Preparation)
As a transparent resin plate, a laminate (pencil hardness 2H, overall thickness 1 mm, PMMA thickness 100 μm) in which polymethyl methacrylate (PMMA), polycarbonate (PC) and polymethyl methacrylate (PMMA) are laminated in this order is used. Prepared.
As irregular-shaped reactive silica fine particles, fine particles having an average primary particle size of 50 nm and having a methacrylate group as a reactive functional group (a dispersion having a solid content concentration of 40% by weight) were prepared. The irregular-shaped reactive silica fine particles are fine particles in which a plurality of spherical silicas are bonded by a covalent bond.
Pentaerythritol triacrylate (PETA) was prepared as a binder component. Irgacure 907 manufactured by Ciba Japan Co., Ltd. was prepared as a polymerization initiator.
X-71-1203M (manufactured by Shin-Etsu Chemical Co., Ltd., Si—F surfactant) was prepared as surfactant A that imparts antifouling properties.
Propylene glycol monomethyl ether acetate (PGMEA) was prepared as a solvent.

(Preparation of curable resin composition)
A curable resin composition was prepared with the following composition.
Reactive silica fine particle dispersion: 20 parts by weight (solid content concentration 40% by weight)
Binder component: 30 parts by weight Polymerization initiator: 0.15 parts by weight Solvent: 48 parts by weight

(Preparation of hard coat layer)
A curable resin composition is applied to one side of the transparent resin plate by a spin coating method, dried in a hot oven at a temperature of 80 ° C. for 180 seconds, the solvent in the coating film is evaporated, and the accumulated light amount is 1000 mJ / A hard coat layer having a thickness of 10 μm was formed by curing the coating film by irradiation so as to be cm ² . This obtained the protector for evaluation.

[Examples 2 to 13, Comparative Examples 1 and 2]
A protective body for evaluation was obtained in the same manner as in Example 1 except that the composition of the curable resin composition and the thickness of the hard coat layer were changed as shown in Table 1. The composition of the curable resin composition was adjusted so that the ratio of the components other than the reactive silica fine particle dispersion was constant.
In Example 9, fine particles having an average primary particle size of 12 nm and a methacrylate group as a reactive functional group (dispersion having a solid concentration of 40% by weight) were prepared as spherical reactive silica fine particles.
Moreover, in the comparative example 2 and Examples 5-8, the Ciba Japan Co., Ltd. product and Irgacure 184 were prepared as a polymerization initiator.
In Example 13, TF1682 (manufactured by DIC, Si-F surfactant) was prepared as the surfactant B imparting printability.

[Examples 14 to 20]
A protective body for evaluation was obtained in the same manner as in Example 3 except that the configuration, thickness, and hardness of the transparent resin plate were changed as shown in Table 2.

[Evaluation 1]
(Pencil hardness test)
After the test protectors obtained in Examples 1 to 20 and Comparative Examples 1 and 2 were conditioned for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%, the test pencil specified by JIS-S-6006 was used. The pencil hardness test (4.9 N load) specified in JIS K5600-5-4 (1999) was used to evaluate the highest pencil hardness without scratches. The results are shown in Tables 1 and 2.

(Contact angle measurement)
Measurement of the contact angle of water droplets in the evaluation protectors obtained in Examples 1 to 20 and Comparative Examples 1 and 2 using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) And 30 seconds after dropping a water droplet). The results are shown in Tables 1 and 2.

  As shown in Table 1, it was confirmed that the pencil hardness of the hard coat layer was improved by adding reactive silica fine particles. Moreover, in Examples 1-10, by using surfactant A which provides antifouling property, a contact angle became 100 degrees and it was confirmed that it is useful as a 1st hard-coat layer. In Examples 12 and 13, by using the surfactant B that imparts printability, the contact angle was 70 °, which was confirmed to be useful as the second hard coat layer. On the other hand, as shown in Table 2, in Examples 14 to 20, it was confirmed that even when the configuration of the transparent resin plate was changed, the hard coat layer had good pencil hardness. Furthermore, by using the surfactant A that imparts antifouling properties, the contact angle was 100 °, which was confirmed to be useful as the first hard coat layer.

[Example 21]
The hard coat layer of Example 3 was formed on one side of the transparent resin plate, and the hard coat layer of Example 12 was formed on the other side of the transparent resin plate to obtain an evaluation protector.

[Example 22]
The hard coat layer of Example 3 was formed on one side of the transparent resin plate, and the hard coat layer of Example 13 was formed on the other side of the transparent resin plate to obtain an evaluation protector.

[Evaluation 2]
When the curvature of the protection body for evaluation (10 cm × 10 cm) obtained in Examples 21 and 22 was measured, both were 200 μm or less. On the other hand, the warp in the longitudinal direction of the protective body for evaluation obtained in Example 3 was 1 mm. Thus, it was confirmed that warpage is suppressed by forming hard coat layers on both surfaces of the transparent resin plate.

DESCRIPTION OF SYMBOLS 1 ... Transparent resin board 1a ... Inner transparent resin layer 1b ... Outermost transparent resin layer 2a ... 1st hard coat layer 2b ... 2nd hard coat layer 10 ... Protector 20 ... Touch panel sensor 100 ... Touch panel module

Claims (2)

A transparent resin plate, a first hard coat layer formed on one surface side of the transparent resin plate, and a second hard coat layer formed on the other surface side of the transparent resin plate,
The first hard coat layer has a polymer containing reactive fine silica particles and a first binder component, and a first surfactant that imparts antifouling properties,
The second hard coat layer includes a polymer containing a second binder component, and a second surfactant that imparts printability. A touch panel sensor and a protector formed on the touch panel sensor;
The touch panel module according to claim 1, wherein the protector is the protector according to claim 1.

Images