KR101413900B1 - Abrasion-resistant resin laminate, material for front cover of display and image display device - Google Patents

Abstract

[PROBLEMS] To provide a scratch resistance resin laminate having a scratch resistance function as a high surface hardness while eliminating problems such as warping and productivity.
[MEANS FOR SOLVING PROBLEMS] A curable resin composition comprising a curable resin layer (B) comprising an organic-inorganic hybrid hard coating on both sides or one side of an acrylic resin layer (A) containing an acrylic resin as a main component, The layer (A) is a hard resin (a) having a hard dispersed phase in an acrylic resin layer matrix, and the organic-inorganic hybrid coating agent is composed of a curable resin composition containing an inorganic component having a reactive functional group, Wherein the thickness of the ground layer (B) is in the range of 5 to 15 mu m and the surface hardness of the surface on which the curable resin layer (B) is laminated is 7H or more.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an abrasion resistant resin laminate, a front cover material of a display, and an image display device.

The present invention relates to a surface protection panel for use on a front surface side (view side) of an image display apparatus, and particularly to a surface protection panel which can be suitably used as a front cover material for a cellular phone or a liquid crystal pen tablet having a touch panel function, .

BACKGROUND ART [0002] Conventionally, in the field of a cover material for displays of electronic apparatuses, glass has been widely used in view of hardness, heat resistance and transparency.

However, since the glass is easily broken by the impact, and the weight of the glass itself is also heavy, substitution with plastic has been studied.

In recent years, various electronic apparatuses and apparatuses have been made more compact, lighter, higher in performance, and lowered in price, and the use conditions of resin molded articles including display covers have become stricter. In order to cope with the production of low- ) Resin sheet having high productivity because of excellent processability is strongly demanded.

In these applications, acrylic resins are widely used because of their high transparency and excellent surface hardness.

However, since acrylic resins are very brittle, their processing methods are generally performed by cutting, and they can not be said to be highly productive.

In addition, when an acrylic resin is used, there is a problem that, for example, when it is contacted with a hard material such as a steel wool, the abrasion resistance of the matrix resin portion is low,

Thus, for example, in Patent Document 1, an acrylic resin layer mainly composed of an acrylic resin having a thickness of 10 to 40 mu m is laminated on both sides or one side of a resin sheet made of a resin material containing a polycarbonate resin as a main component, A polycarbonate resin laminated sheet for punching has been proposed in which a hard coating layer is laminated on a resin layer to have a total thickness of 0.2 to 2.0 mm. Such a resin laminated sheet has excellent punching workability and therefore has high productivity and excellent scratch resistance.

In Patent Document 2, the thickness of the layer including the acrylic resin constituting the laminate including the polycarbonate resin and the total thickness of the laminate are controlled within a specific range, and furthermore, There has been proposed a laminate comprising a polycarbonate resin suitable for a liquid crystal display cover having a balance of surface hardness, particularly pencil hardness and impact resistance, by hard coating the resin-containing layer and the substrate containing the polycarbonate resin .

As described above, in order to improve the scratch resistance of the surface of the resin molded article using an acrylic resin, a method of laminating a hard coat layer composed of an ultraviolet curable resin or the like to a predetermined thickness is generally used. According to this resin laminate, the surface hardness such as scratch resistance and abrasion resistance is improved by the laminated scratch-resistant resin layer.

Patent Document 3 proposes a scratch-resistant resin laminate in which a scratch-resistant resin layer having a thickness of 1 to 5 m is laminated on a substrate composed of an acrylic resin as a thermoplastic matrix resin containing a hard dispersed phase. This antiscratching resin laminate has such a property that even if the base material and the resin material constituted by the acrylic resin are different from each other, there is no case where warping, bending, peeling, or the like occurs due to curing and shrinkage of the resin.

Japanese Patent Application Laid-Open No. 2008-049623 International Publication Pamphlet WO 2008/047940 Japanese Patent Application Laid-Open No. 2007-296711

In the resin laminate disclosed in the above Patent Documents 1 and 2, when a hard coating layer is laminated on a substrate made of an acrylic resin or the like, there is a problem that warping, bending, peeling, or the like occurs along with curing and shrinkage of the resin there was.

The anti-scratch resin disclosed in Patent Document 3 has a structure in which a thermoplastic resin as a matrix resin contains a hard resin obtained by radical polymerization as a dispersed phase.

The dispersed phase improves the scratch resistance of the resin molded article, but there is still room for improvement in terms of surface hardness such as pencil hardness.

Therefore, an object of the present invention is to provide an antiscratching resin laminate having an antiscratching function as a high surface hardness while eliminating the problem of warping and bending.

The present invention is characterized in that it comprises a structure in which a curable resin layer (B) comprising an organic-inorganic hybrid hard coating agent is laminated on both sides or one side of an acrylic resin layer (A) containing an acrylic resin as a main component A scratch-resistant resin laminate is proposed.

The present invention is also characterized in that an organic-inorganic hybrid hard coating agent is contained on at least one side of a resin laminate on both sides or one side of a resin substrate (C), in which an acrylic resin layer (A) containing an acrylic resin as a main component is laminated And a curable resin layer (B) is laminated on the surface of the resin layer.

The scratch resistance resin laminate proposed by the present invention is provided with a curable resin layer (B) containing an organic-inorganic hybrid hard coating agent so as to have a scratch resistance function as a high surface hardness .

More preferably, by applying the curable resin layer (B) containing the organic-inorganic hybrid hard coating agent in the resin laminate having the specific structure, excellent punching workability is imparted, and scratch resistance function .

Therefore, the present scratch-resistant resin laminate can be suitably used as a front cover material of a liquid crystal display, particularly as a front cover material of a cellular phone or a liquid crystal pen tablet having a touch panel function.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a view showing an example of a scratch-resistant resin laminate according to an embodiment of the present invention; FIG.

Hereinafter, a scratch-resistant resin laminate (referred to as " present resin laminate ") as an example of an embodiment of the present invention will be described. However, the present invention is not limited to the present resin laminate.

<This resin laminate>

This resin laminate has a structure in which a curable resin layer (B) comprising an organic-inorganic hybrid hard coating agent is laminated on both sides or one side of an acrylic resin layer (A) containing an acrylic resin as a main component.

More preferably, the present resin laminate is a laminate obtained by laminating at least one surface of a resin laminate on which an acrylic resin layer (A) containing an acrylic resin as a main component is laminated on both sides or one side of a resin substrate (C) And a curable resin layer (B) containing an inorganic hybrid hard coating agent.

&Lt; Acrylic resin layer (A) >

The acrylic resin layer (A) is a layer containing an acrylic resin as a main component.

Examples of the monomer constituting the acrylic resin include methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydrolyzed (meth) acrylate, (Meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (Meth) acryloyloxyethyl, maleic acid 2- (meth) acryloyloxyethyl, phthalic acid 2- (meth) acryloyloxy (meth) acrylate, 2- (Meth) acrylate, dimethylaminoethyl (meth) acrylate, diethyl (meth) acrylate, ethylhexylphthalate, 2- Aminoethyl (meth) acrylate, and the like.

These may be used alone or in combination of two or more. Examples of other monomers that can be polymerized with these acrylic monomers include polyolefin monomers, vinyl monomers, and the like.

The acrylic resin layer (A) is preferably composed of a hard resin layer (a) having a pencil hardness of 3H or more. By forming the acrylic resin layer (A) with such a high surface hardness, it is possible to obtain an advantage that an extremely high surface hardness can be imparted to the resin laminate.

From this viewpoint, the pencil hardness of the acrylic resin layer (A) is more preferably 4H or more, and more preferably 5H or more.

As a preferred method of setting the pencil hardness of the acrylic resin layer (A) to 3H or more, a method of including a hard dispersed phase in the acrylic resin matrix of the acrylic resin layer (A) can be mentioned.

More specifically, there can be mentioned a method of forming an acrylic resin layer (A) by a hard resin layer (a) comprising an acrylic resin containing a hard dispersed phase material superior in heat resistance or scratch resistance to acrylic resin.

As the hard dispersive phase material, a thermosetting resin can be enumerated. Specifically, in addition to a polycondensation or an addition condensation resin such as a phenol resin, an amino resin, an epoxy resin, a silicone resin, a thermosetting polyimide resin and a thermosetting polyurethane resin, Acrylic resins, vinyl ester-based resins, unsaturated polyester-based resins, and diallyl phthalate-based resins. However, the present invention is not limited thereto. The thermosetting resins may be used alone or in combination of two or more. The thermosetting resin may be used in combination with a thermoplastic resin having an unsaturated bond capable of crosslinking.

The shape of the hard dispersed phase may be particulate, spherical, linear, fibrous, or the like, and is preferably spherical in that it is easily dispersed evenly in the acrylic resin as the thermoplastic matrix resin. However, the present invention is not limited to this.

The particle size of the hard dispersed phase is appropriately set according to the purpose of use, application, etc. of the present resin laminate, and is preferably 0.1 to 1000 mu m. The blending amount of the hard dispersed phase in the acrylic resin layer (A) is appropriately determined depending on the purpose of use, application, etc. of the resin laminate, and is preferably 0.1 to 60 wt%.

The method for incorporating the hard dispersed phase in the acrylic resin layer (A) is not particularly limited, and for example, the following method can be mentioned.

a) A thermosetting resin material constituting a hard dispersed phase is added to an acrylic resin material.

b) Next, a hard dispersed phase can be constituted by melting and kneading, molding into a predetermined shape, and phase separation and crosslinking. The thermosetting resin may be previously molded into particulate form, added to the acrylic resin, and kneaded and molded at a temperature at which the thermosetting resin is not dissolved.

(The thickness of the acrylic resin layer (A)

The thickness of the acrylic resin layer (A) is preferably 40 占 퐉 or more. When the layer thickness of the acrylic resin layer (A) is 40 탆 or more, there is no possibility that the effect of improving the scratch resistance due to the contribution of the acrylic resin layer is not obtained. From this point of view, the thickness of the acrylic resin layer (A) is more preferably 50 m or more. From the viewpoint of moldability, the thickness of the acrylic resin layer (A) is preferably 200 占 퐉 or less, more preferably 100 占 퐉 or less.

&Lt; Curable resin layer (B) >

This resin laminate has a curable resin layer (B). The curable resin layer (B) contains an organic-inorganic hybrid hard coating agent and is a layer which imparts high scratch resistance to the present resin laminated body without causing warping or bending.

The curable resin layer (B) can be formed by laminating, for example, an organic-inorganic hybrid hard coating agent on a different layer as a coating film. However, the present invention is not limited to this method.

As a method of laminating with other layers, a known method is used. Examples of the coating method include a lamination method using a cover film, a dip coating method, a natural coating method, a reverse coating method, a comma coater method, a roll coating method, a spin coating method, a wire bar method, A gravure coating method and the like. Alternatively, a method of laminating the curable resin layer (B) on another layer may be employed, for example, by using a transfer sheet formed by adhering a curable resin layer (B) to a release layer.

(Organic / inorganic hybrid coating agent)

As the organic-inorganic hybrid coating agent, those containing a curable resin composition containing an inorganic component having a reactive functional group can be cited.

Such an organic-inorganic hybrid coating agent can be prepared by using an inorganic component having a reactive functional group, for example, by copolymerizing and crosslinking the inorganic component with a radical polymerizable monomer to form an organic-inorganic hybrid Based coating agent, hardening shrinkage is less likely to occur and higher scratch resistance can be exhibited.

More preferably, from the viewpoint of curing shrinkage, an organic-inorganic hybrid coating agent containing ultraviolet-reactive silica as an inorganic component having a reactive functional group can be mentioned.

More preferably, organic-inorganic hybrid coating agents including ultraviolet-reactive colloidal silica can be mentioned.

Further, examples of the radical polymerizable monomer include polyfunctional (meth) acrylates. Examples of the bifunctional di (meth) acrylate include ethylene oxide modified diacrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acrylate (Meth) acrylate, bisphenol A ethylene oxide modified diacrylate, dimethylol-tricyclodecane di (meth) acrylate, tripropylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, epoxy (meth) diacrylate, and urethane (meth) diacrylate.

Examples of polyfunctional (meth) acrylates having three or more functional groups include pentaerythritol hexaacrylate, ditrimethylol propane tetraacrylate, pentaerythritol ethoxy tetraacrylate, trimethylol propane tri (meth) acrylate (Meth) acrylate, urethane tetra (meth) acrylate, urethane tetra (meth) acrylate, urethane hexa (meth) acrylate, polyester tetra Ester hexa (meth) acrylate, and the like.

Further, monofunctional (meth) acrylates can be suitably added for the purpose of adjusting hardening shrinkage and viscosity in hard coating and improving solubility of small amounts of additives. Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, tert-butyl (meth) acrylate, isobornyl (meth) acrylate, octyl Acrylate, decyl (meth) acrylate, methoxypolyethylene (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydroperfuryl (meth) acrylate and phenoxyethyl (meth) acrylate.

The content of the inorganic component having a reactive functional group in the organic-inorganic hybrid coating agent is preferably 5% by mass or more and less than 65% by mass, more preferably 10% by mass or less but less than 50% by mass from the viewpoints of surface hardness, transparency and punching workability And most preferably from 15% by weight to less than 50% by weight.

(Surface conditioning component)

The curable resin layer (B) preferably includes a leveling agent as a surface conditioning component.

As the leveling agent, a silicon leveling agent, an acrylic leveling agent and the like can be mentioned, and it is particularly preferable to have a reactive functional group at the terminal thereof, more preferably a reactive functional group having two or more functions.

Specifically, a polyether-modified polydimethylsiloxane having an acryl group (e.g., &quot; BYK-UV 3500 &quot;, &quot; BYK-UV 3530 &quot; manufactured by Big Chemie Japan KK) having a double bond at both ends , And polyester-modified polydimethylsiloxane having an acryl group ("BYK-UV 3570" manufactured by Big Chem Japan Co., Ltd.), each having a total of four double bonds at the ends.

Among them, a polyester-modified polydimethylsiloxane having an acryl group is particularly preferable, which has a stable haze value and contributes to improvement in scratch resistance.

(Other components)

The curable resin layer (B) preferably includes a lubricant.

Examples of the lubricant include silicon-based compounds, fluorine-based compounds, and mixed compounds thereof. By adding these, the slidability can be improved.

In addition to the above, the ultraviolet absorber, light stabilizer, antioxidant, antistatic agent and the like may be added to the curable resin layer (B), if necessary.

(Thickness of the curable resin layer (B)

The thickness of the curable resin layer (B) is preferably in the range of 5 to 15 mu m. When the thickness is 5 탆 or more, the effect of improving the scratch resistance by the curable resin layer (B) is sufficiently obtained. On the other hand, when the thickness is 15 탆 or less, the ultraviolet curable resin constituting the curable resin layer (B) There is no fear of bending, bending, peeling, and the like. Further, there is no fear that the transparency is significantly impaired by the ultraviolet ray hardenable resin layer.

This resin laminate can attain high hardness even in a thin resin laminate due to the synergistic effect of the acrylic resin layer (A) containing the hard dispersed phase and the curable resin layer (B). For example, when the thickness of the acrylic resin layer (A) is 200 m, which is the upper limit of the above-mentioned preferable range, and the thickness of the curable resin layer (B) is less than 5 m, Hardness can not be achieved. On the contrary, when the thickness of the acrylic resin layer (A) is 40 mu m, which is the lower limit of the preferable range described above, when the thickness of the curable resin layer (B) exceeds 15 mu m, Or bending may occur. As described above, in order to achieve high hardness in the present resin laminate, it is preferable that the lamination ratio of the acrylic resin layer (A) is 50 占 퐉 or more and 200 占 퐉 or less and the thickness of the curable resin layer And particularly preferably from 5 탆 to 15 탆.

In general, it is known that the curable resin layer shrinks at the time of curing, and curl may be formed when the layer is laminated with another layer. Since the ratio of the shrinkage of the curable resin layer tends to be proportional to the thickness of the curable resin layer, achieving the hardness only by the thickness of the curable resin layer is not practical from the curl point of view. The curl accompanied by the curing shrinkage of the resin laminate is preferably 3 mm or less, more preferably 2 mm or less. From the viewpoint of suppressing this curling, it is preferable to set the thickness ratio of the acrylic resin layer (A) and the curable resin layer (B) within the above-mentioned range.

&Lt; Resin substrate (C) >

The resin substrate (C) is a layer which functions to impart punching workability to the resin laminate. In view of this, as the resin substrate (C), a resin such as polycarbonate (PC) resin, triacetyl cellulose (TAC) resin, polyethylene terephthalate (PET) resin, polymethylmethacrylate (PMMA) It is preferably formed of a resin composition containing at least one of a phenol resin, a phenol resin, a phenol resin, a phenol resin, a phenol resin, a phenol resin, a phenol resin, a phenol resin, a phenol resin, a phenol resin,

In a preferable use of the resin laminate, the resin base material (C) is preferably composed of a transparent resin.

Particularly, the resin substrate (C) is preferably formed of a polycarbonate resin in view of transparency, impact resistance, heat resistance and the like.

The polycarbonate resin is obtained, for example, by an interfacial polymerization method in which an aromatic dihydroxy compound is reacted with a small amount of a polyhydroxy compound together with a phosgene.

Examples of the aromatic dihydroxy compound include bisphenol A synthesized from bisphenol and acetone.

In addition, bisphenol A can be used as a raw material and can be produced by an ester exchange method, a pyridine method, or the like.

Further, examples of the polyester resin obtained by polymerization of bisphenol A with a dicarboxylic acid derivative, for example, a polyester carbonate obtained by copolymerization such as tetra (iso) phthalic acid dichloride, a derivative of bisphenol A such as tetramethylbisphenol A, can do.

The molecular weight of the polycarbonate resin is preferably such that the viscosity is such that the sheet can be produced by ordinary extrusion molding. Specifically, the viscosity average molecular weight is preferably 15,000 to 400,000, more preferably 20,000 to 35,000, Lt; / RTI &gt;

If the molecular weight is smaller than this, the impact strength of the sheet obtained from the composition becomes low, which is not preferable. On the other hand, if the molecular weight is larger than this, the fluidity is lowered and the extrusion moldability may be deteriorated.

&Lt; Configuration of the present resin laminate >

This resin laminate should have a curable resin layer (B) comprising an acrylic resin layer (A) and an organic-inorganic hybrid coating agent. Also preferably, a resin base material (C) is further provided.

More specifically, (B) / (A), (B) / (A) / (B), (A), (B), (B), (C), (A), (B) / (B). Among these constitution, a constitution in which the curable resin layer (B) is laminated on both sides or one side of the acrylic resin (A) is preferable, and the constitution (B) / (A) / (C) ) / (B) is most preferable.

Fig. 1 shows the structure of one embodiment of the present resin laminate. In Fig. 1 (a), a resin laminate having an acrylic resin layer 13 laminated on one side of the resin base material 12 is cured And the resin layer 14 is laminated thereon.

According to such a configuration, there is an advantage that a high surface hardness can be exhibited even when the thickness of the curable resin layer is as thin as 5 to 15 mu by the synergistic effect of the acrylic resin layer 13 and the curable resin layer 14 .

1 (b), an antiscratching resin laminate 11 having a structure in which a curable resin layer 14 is laminated on both sides of a resin laminate in which an acrylic resin layer 13 is laminated on one side of a resin base material 12 ). According to this structure, since the curable resin layer 14 is also laminated on the resin base material 12, there is an advantage such that occurrence of process scratches on the resin base material 12 can be suppressed. On the other hand, the curable resin layer on the side of the resin base material 12 formed to suppress the occurrence of process flaws may be formed by a normal hard coat layer.

<Manufacturing Method>

The production method of the resin laminate is not particularly limited, and a known method can be employed.

The production apparatus of this resin laminate is constituted by, for example, a main extruder for extruding a polycarbonate resin and a sub extruder for extruding an acrylic resin constituting an acrylic resin layer. Usually, the secondary extruder is smaller than the main extruder.

The temperature condition of the main extruder is usually 230 to 290 ° C, preferably 240 to 280 ° C, and the temperature condition of the secondary extruder is usually 220 to 270 ° C, preferably 230 to 260 ° C. It is also preferable to provide a polymer filter on the upstream side of the T-die of the extruder in order to remove foreign matter from the resin.

Known methods such as a feed block method and a multi-manifold method can be used as a method of laminating the two kinds of molten resins by co-extrusion. In this case, the molten resin laminated with the feed block is guided to a sheet molding die such as a T-die to be molded into a sheet, and then the surface is introduced into a mirror-finished molding roll (metal elastic roll or polishing roll) do.

The sheet-form molding is subjected to mirror-surface finishing and cooling during passing of the molding roll, and a laminate is formed.

Further, in the case of the multi-manifold die, the molten resin laminated in the die is likewise molded into a sheet form inside the die, followed by surface finishing and cooling by a forming roll, thereby forming a laminate. The die temperature is usually 210 to 300 占 폚, preferably 230 to 280 占 폚, and the forming roll temperature is usually 100 to 190 占 폚, preferably 110 to 180 占 폚. The roll may be a vertical roll or a horizontal roll, as appropriate.

<Applications>

This resin laminated body is useful as a front cover material such as a surface protective panel which is disposed and used on the front side (view side) of an image display apparatus, in particular, a cellular phone or a liquid crystal pen tablet having a touch panel function.

<Explanation of Terms>

In general, the term &quot; film &quot; means a thin and flat product having an extremely small thickness and a maximum thickness arbitrarily limited in length and width, and is usually supplied in the form of a roll (Japanese Industrial Standard JIS K6900) Refers to a product that is thin and generally thin in comparison to its length and width, as defined by JIS. However, since the boundary between the sheet and the film is not certain and it is not necessary to distinguish the two from each other in the present invention, the term &quot; sheet &quot;Quot; and &quot; film &quot;

In the present specification, the expression &quot; main component &quot; includes the meaning allowing other components to be contained in the range not interfering with the function of the main component, unless otherwise specified.

At this time, although the content of the main component is not specified, the main component (when the two or more components are the main components, the total amount thereof) is 50 mass% or more, preferably 70 mass% or more, particularly preferably 90 mass% Or more (including 100%).

In the present invention, "X to Y" (where X and Y are arbitrary numbers) means "not less than X and not more than Y" unless otherwise specified, and "preferably larger than X" Quot; is smaller than Y &quot;.

In the present invention, when expressed as &quot; X or more &quot; (X is an arbitrary number), unless specifically stated otherwise, &quot; preferably larger than X &quot;Quot; is preferably &quot; smaller than Y &quot; unless otherwise specified.

Example

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto, and various applications are possible without departing from the technical idea of the present invention.

<Measurement and Evaluation Method>

First, measurement methods and evaluation methods of various physical properties of samples obtained in Examples and Comparative Examples are described.

(Evaluation of surface hardness)

With respect to the resin laminate of Examples and Comparative Examples, the pencil hardness at the surface was measured according to JIS K 5600-5-4.

(Evaluation of scratch resistance)

For the resin laminate of Examples and Comparative Examples, the surface (curable resin layer side) of the resin laminate was rubbed 50 times with a load of 1000 g using # 0000 steel wool, and the presence or absence of scratches was visually observed. On the other hand, in Table 1, the symbol &quot; No scratches &quot; indicates &quot; Scratches, but the practical level &quot;

<Punching Workability>

Resin Laminates of Examples and Comparative Examples Test specimens of 20 cm square were subjected to a punching test using a dumbbell blade of JIS K 6251 with a screw press manufactured by Toyo Seiki Seisakusho Co., The evaluation was made based on the presence of cracks on the punched sample pieces and the base material or the breakage of the base material. The symbol &quot; No cracks or cracks &quot;, and the letters &quot; Cracked or cracked &quot;

<Curl Test>

A cured resin layer was formed by using the same method as described in each of the Examples and Comparative Examples, using an A4 size PET film (manufactured by Mitsubishi Plastics, trade name &quot; Diafoil &quot; The central portion of each sample was cut into 10 cm squares and used as a test sample. In the evaluation, warpage at four corners was regularly measured, and the average value of the four points was used as a curl value in the test sample.

&Lt; Example 1 >

A layer made of a mixture of 80 parts by mass of a polycarbonate resin (trade name "U.Philon S1000" available from Mitsubishi Engineering Plastics Co., Ltd.) as a base resin and 20 parts by mass of PCTG (trade name, SKYGREEN J2003 made by SK Chemicals Co., Ltd.) Extruded so that the thickness of the base resin layer was 560 占 퐉, the thickness of the acrylic resin layer was 140 占 퐉, and the thickness of the layered product was 700 占 퐉 by an extrusion molding machine to form a layer made of resin (trade name "Altuglas HT121" The sieve was molded. The extrusion conditions were as follows: the extrusion temperature of the acrylic resin layer was 240 占 폚; the extrusion temperature of the base resin layer was 265 占 폚; and the roll temperatures were R1 = 110 占 폚, R2 = 120 占 폚 and R3 =

10 parts by mass of an organic / inorganic hybrid ultraviolet-curable hard coating agent (trade name: "EKS1105", trade name: an inorganic component (silica) having an ultraviolet-reactive functional group (silica) content: 15 to 25% by mass) Irgacure 184 (Ciba Japan Co., Ltd.) 0.2 parts by mass, and the mixed solution MEK 2 parts by weight of a coating using a bar coater and exposed in a dried 3 minutes at 70 ℃, the exposure amount of 500mJ / cm ^2, curing after drying Whereby a resin laminate 1 having a resin layer thickness of 5 탆 was obtained.

&Lt; Example 2 >

An organic / inorganic hybrid ultraviolet ray hardening hard coating agent (trade name: "UVHC7800", an inorganic component (silica) having an ultraviolet reactive functional group: 40 to 50 mass%) was applied to the surface of the acrylic resin layer of the laminate a, applied by a coater, and dried for one minute at 90 ℃, exposed by an exposure amount of 500mJ / cm ^2, the thickness of the curable resin layer after drying was obtained 6㎛ the resin laminate 2.

&Lt; Example 3 >

As a leveling agent, the procedure of Example 2 was repeated except that 5 parts of polyester-modified polydimethylsiloxane having an acrylic group (trade name &quot; BYK-UV 3570 &quot;, trade name, Similarly, a resin laminate 3 having a thickness of 6 占 퐉 of the curable resin layer after drying was obtained.

<Example 4>

(Trade name: EXCERATE RUA-069VE, content of inorganic component (silica) having an ultraviolet-reactive functional group: 5 to 15 mass%) was coated on the surface of the acrylic resin layer of the laminate a, the coating using a bar coater, and dried for one minute at 90 ℃, exposed by an exposure amount of 500mJ / cm ^2, to obtain the thickness of the curable resin after drying 6㎛ the resin laminate 4.

&Lt; Example 5 >

An organic / inorganic hybrid ultraviolet ray hardening hard coating agent (trade name: "UVHC7300", product of Momentive, content of inorganic component (silica) having an ultraviolet-reactive functional group: 10 to 20% by mass) applied by a coater, and dried for one minute at 90 ℃, exposed by an exposure amount of 500mJ / cm ^2, to obtain a resin laminate 5. the thickness of the curable resin layer after drying 6㎛.

&Lt; Example 6 >

A laminate b composed of an acrylic resin layer having a thickness of 700 mu m was molded by an extruder using an acrylic resin having a hard and dispersed phase (manufactured by Arkema, trade name "Altuglas HT121"). The extrusion conditions were an extrusion temperature of 240 占 폚, a roll temperature of R1 = 110 占 폚, R2 = 120 占 폚 and R3 = 125 占 폚.

An organic / inorganic hybrid ultraviolet ray hardening hard coating agent (trade name: "UVHC7800" manufactured by Momentive Co., Ltd., content of inorganic component (silica) having an ultraviolet reactive functional group: 40 to 50 mass%) was laminated on one surface of the laminate b using a bar coater coated, and dried for one minute at 90 ℃, exposed by an exposure amount of 500mJ / cm ^2, the thickness of the curable resin after drying to give a resin laminate 6. 6㎛.

&Lt; Comparative Example 1 &

10 parts by mass of an ultraviolet curable hard coating agent of a main component urethane acrylate (trade name: EXCERATE RUA-066VE, manufactured by Asai Kagaku Kogyo Co., Ltd.), 0.02 parts by mass of Irgacure 184 (manufactured by Chiba Japan) 15 parts by weight of a mixed solution, applied by a bar coater, and dried for 5 minutes at 70 ℃, exposed by an exposure amount of 500mJ / cm ^2, the thickness of the curable resin after drying to give a resin laminate 7. 7㎛ .

&Lt; Comparative Example 2 &

(UVHC1101, manufactured by Momentive Co., Ltd.) was coated on the surface of the acrylic resin layer of the laminate a using a bar coater, dried at 90 占 폚 for 1 minute, and then dried at 500 mJ / cm ² to obtain a resin laminate 8 having a thickness of 8 占 퐉 of the curable resin layer after drying.

&Lt; Comparative Example 3 &

A resin sheet "c" having a thickness of 700 μm was molded by an extrusion molding machine using a polycarbonate resin (trade name "YuPiron S1000" manufactured by Mitsubishi Engineering Plastics Co., Ltd.). The extrusion conditions were an extrusion temperature of 265 占 폚, a roll temperature of R1 = 110 占 폚, R2 = 120 占 폚 and R3 = 125 占 폚.

An organic / inorganic hybrid ultraviolet ray hardening hard coating agent (product name: "UVHC7800", product name: "UVHC7800", content of an inorganic component (silica) having an ultraviolet-reactive functional group: 40 to 50 mass%) was applied to one surface of the resin sheet c using a bar coater coated, and dried for one minute at 90 ℃, exposed by an exposure amount of 500mJ / cm ^2, to obtain a resin laminate 9, the thickness of the curable resin after drying 6㎛.

&Lt; Comparative Example 4 &

A single-layer resin sheet d having a thickness of 700 mu m was formed by an extrusion molding machine using an acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name "Acryphet VH001") having no hardened dispersed phase. The extrusion conditions were an extrusion temperature of 240 占 폚, a roll temperature of R1 = 100 占 폚, R2 = 110 占 폚 and R3 = 125 占 폚.

EXCERATE RUA-066VE ", trade name, manufactured by Asahi Denka Co., Ltd.) was coated on one side of the resin sheet d using a bar coater, dried at 70 ° C for 5 minutes, and then cured at 500 mJ / cm ² To obtain a resin laminate 10 having a thickness of 6 占 퐉 of the cured resin layer after drying.

The evaluation results of the resin laminate 1 to 10 obtained in Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Table 1. For the comprehensive evaluation, the pencil hardness was 7H or more and the value of the curl test was 2 mm or less, and &quot; x &quot;

Thickness of the curable resin layer (占 퐉) Pencil hardness Punching processability Scratch resistance evaluation curl
(mm) Overall assessment Example 1 5 8H ○ ○ 1.5 ○ Example 2 6 8H ○ ○ One ○ Example 3 6 8H ○ ○ One ○ Example 4 6 7H ○ △ 0.5 ○ Example 5 6 7H ○ ○ 0.5 ○ Example 6 6 8H × ○ 0.5 ○ Comparative Example 1 7 7H ○ × 15 × Comparative Example 2 8 7H ○ △ > 15 × Comparative Example 3 6 2H ○ ○ One × Comparative Example 4 6 3H × ○ One ×

From the results shown in Table 1, the urethane acrylate-based ultraviolet-curable hard coating agents of Comparative Example 1 and Comparative Example 2 had a pencil hardness of 7H, but the amount of curl was large, which was not a practical level.

On the other hand, in the embodiment using the organic-inorganic hybrid ultraviolet ray hardening hard coating agent, it has a high pencil hardness and no warping or bending is observed.

Particularly, in the organic-inorganic hybrid UV-curable hard coatings of Examples 1 to 3 and Example 6, a pencil hardness of 8H is achieved.

However, in Comparative Example 3, although the organic-inorganic hybrid ultraviolet-curable hard coating agent was used for the polycarbonate resin, the hardness of the base resin was low and it was not possible to obtain sufficient pencil hardness.

From these results, it is possible to obtain a scratch resistant resin laminate having a higher hardness by laminating a curable resin layer containing an organic-inorganic hybrid hard coat agent on a laminate of an acrylic resin.

On the other hand, in the present embodiment and the comparative example, a PET film was used in order to clarify the difference in the curling test, but it is presumed that the same tendency is also seen in the laminated bodies 1 to 3.

<Curl Test 2>

Using the following laminate d as a resin substrate, a cured resin layer was formed by the same method as that described in each of the Examples and Comparative Examples. The central portion of each sample was cut into 10 cm squares and used as a test sample. In the evaluation, warpage at four corners was regularly measured, and the average value of the four points was used as a curl value in the test sample. On the other hand, the curl value is a value including a thermal expansion coefficient of a raw material.

<Hayes>

The test samples of the resin laminate of Examples and Comparative Examples of 5 cm square were subjected to measurement using NDH5000 (manufactured by Nippon Seishin Kogyo Co., Ltd.) as a test instrument. The test was carried out in accordance with JIS K 7136, and the average value thereof was defined as a haze value in the test sample.

&Lt; Example 7 >

A layer made of a mixture of 80 parts by mass of a polycarbonate resin (trade name "CALIBRE301-4", trade name; product name "CALIBRE301-4" manufactured by Sumitacaster Co., Ltd.) as a base resin and 20 parts by mass of PCTG (trade name, SKYGREEN J2003, manufactured by SK Chemicals Co., Extruded so that the thickness of the base resin layer was 240 占 퐉, the thickness of the acrylic resin layer was 60 占 퐉, and the thickness of the layered product was 300 占 퐉 by an extruder to form a layer comprising the resin ("Altuglas HT121" The sieve was molded. The extrusion conditions were as follows: the extrusion temperature of the acrylic resin layer was 240 deg. C, the extrusion temperature of the base resin layer was 265 deg. C, the roll temperature was R1 = 110 deg. C, R2 = 115 deg.

10 parts by mass of an organic-inorganic hybrid ultraviolet-curable hard coating agent (trade name: "EKS1105", trade name: an inorganic component (silica) having an ultraviolet-reactive functional group (silica) content: 15 to 25% by mass) Irgacure 184 (Ciba Japan Co., Ltd.) 0.2 parts by mass, and the mixed solution MEK 2 parts by weight of a coating using a bar coater and exposed in a dried 3 minutes at 70 ℃, the exposure amount of 500mJ / cm ^2, curing after drying Whereby a resin laminate 11 having a resin layer thickness of 12 占 퐉 was obtained.

&Lt; Example 8 >

An organic / inorganic hybrid ultraviolet-curable hard coating agent (trade name: "UVHC7800" manufactured by Momentive Co., Ltd., content of an inorganic component (silica) having an ultraviolet-reactive functional group: 40 to 50 mass%) was placed on the surface of the acrylic resin layer of the laminate d, applied by a coater, and dried for one minute at 90 ℃, exposed by an exposure amount of 500mJ / cm ^2, to obtain the thickness of the curable resin after drying 12㎛ resin laminate 12.

&Lt; Example 9 >

As a leveling agent, the procedure of Example 2 was repeated except that 5 parts of polyester-modified polydimethylsiloxane having an acrylic group (trade name &quot; BYK-UV 3570 &quot;, trade name, Similarly, a resin laminate 13 having a thickness of 12 占 퐉 of the curable resin layer after drying was obtained.

&Lt; Example 10 >

EXCERATE RUA-069VE ", an inorganic component (silica) content having an ultraviolet-reactive functional group: 5 to 15% by mass) was coated on the surface of the acrylic resin layer of the laminate d and an organic / inorganic hybrid ultraviolet- the coating using a bar coater, and dried for one minute at 90 ℃, exposed by an exposure amount of 500mJ / cm ^2, to obtain a resin laminate 14, the thickness of the curable resin layer after drying 12㎛.

&Lt; Example 11 >

An organic / inorganic hybrid ultraviolet curable hard coating agent (trade name: "UVHC7300" manufactured by Momentive Co., Ltd., content of inorganic component (silica) having an ultraviolet reactive functional group: 10 to 20% by mass) was applied to the surface of the acrylic resin layer of the laminate d, Coated with a coater, dried at 90 캜 for 1 minute, and exposed at an exposure amount of 500 mJ / cm ² to obtain a resin laminate 15 having a thickness of 12 탆 of the cured resin layer after drying.

&Lt; Comparative Example 5 &

10 parts by mass of an ultraviolet curable hard coating agent of a main component urethane acrylate (trade name: EXCERATE RUA-066VE, manufactured by Asai Kagaku Kogyo Co., Ltd.), 0.02 parts by mass of Irgacure 184 (manufactured by Chiba Japan) 15 parts by weight of a mixed solution, applied by a bar coater, and dried for 5 minutes at 70 ℃, exposed by an exposure amount of 500mJ / cm ^2, to obtain the thickness of the curable resin after drying 12㎛ resin laminate 16 .

&Lt; Comparative Example 6 >

(UVHC1101, manufactured by Momentive Co., Ltd.) as a main component urethane acrylate was coated on the surface of the acrylic resin layer of the laminate d using a bar coater, dried at 90 占 폚 for 1 minute, and then dried at 500 mJ / cm ² to obtain a resin laminate 17 having a thickness of 12 占 퐉 of the cured resin layer after drying.

The evaluation results of the resin laminate 11 to 17 obtained in Examples 7 to 11 and Comparative Examples 4 to 5 are shown in Table 2. For the comprehensive evaluation, the pencil hardness was 7H or more and the value of the curl test was 2 mm or less, and &quot; x &quot;

Of the curable resin layer
Thickness (㎛) Pencil hardness Punching processability Scratch resistance evaluation curl
(mm) Hayes
(%) Overall assessment Example 7 12 9H ○ ○ 0.5 0.43 ○ Example 8 12 9H ○ ○ 0.5 0.38 ○ Example 9 12 9H ○ ○ 0.5 0.36 ○ Example 10 12 8H ○ △ 1.0 0.44 ○ Example 11 12 8H ○ ○ 0.5 0.39 ○ Comparative Example 5 12 7H ○ × 5.0 0.53 × Comparative Example 6 12 7H ○ △ 3.5 0.46 ×

From the results shown in Table 2, it was confirmed that the urethane acrylate-based ultraviolet-curable hard coatings of Comparative Example 5 and Comparative Example 6 did not reach practical levels in terms of scratch resistance and curl.

On the other hand, in Examples 7 to 11, there was almost no curl, and in spite of the thin film base material having a thickness of 300 mu m, a laminate with a high hardness exceeding 8H in pencil hardness was obtained. In particular, in Examples 7 to 9, the pencil hardness of 9H achieves the highest level of surface hardness, and in Example 9, the haze value is obtained by adding a leveling agent.

In order to confirm the moldability of the resin laminate, the following test of moldability was carried out.

&Lt; Moldability >

The resin laminate of Example 12 and Comparative Example 7 was subjected to vacuum molding using an A4 size test sample. The molding conditions were: a molding temperature of 110 deg. C, a vacuum pressure of 0.1 MPa, a molding time of 10 seconds, R = 2 mm at the corners of the mold, and a depth of tightening of 20 mm. In the evaluation, samples after molding are visually evaluated, &quot; No breakage &quot;, and X indicates &quot; Breakage &quot;, respectively.

&Lt; Example 12 >

A layer made of a mixture of 80 parts by mass of a polycarbonate resin (trade name "CALIBRE301-4", trade name; product name "CALIBRE301-4" manufactured by Sumitacaster Co., Ltd.) as a base resin and 20 parts by mass of PCTG (trade name, SKYGREEN J2003, manufactured by SK Chemicals Co., Extruded so that the thickness of the base resin layer was 105 占 퐉, the thickness of the acrylic resin layer was 20 占 퐉, and the thickness of the laminated body was 125 占 퐉 by an extruder to form a layer comprising a resin (trade name "Altuglas HT121" The body was molded. The extrusion conditions were as follows: the extrusion temperature of the acrylic resin layer was 240 deg. C, the extrusion temperature of the base resin layer was 265 deg. C, the roll temperatures were R1 = 110 deg. C, R2 = 110 deg.

An organic-inorganic hybrid ultraviolet-curable hard coating agent (trade name: "UVHC7800F" manufactured by MOMENTIVE, an inorganic component (silica) inorganic component having an ultraviolet reactive functional group: 30 to 40 mass%) was applied to the surface of the acrylic resin layer of the laminate e, Dried at 90 DEG C for 1 minute and exposed at an exposure amount of 500 mJ / cm &lt; ² &gt; to obtain a resin laminate 18 having a thickness of 10 mu m after cured resin layer after drying.

&Lt; Comparative Example 7 &

10 parts by mass of an ultraviolet curable hard coating agent (trade name "EXCERATE RUA-066VE", trade name, manufactured by ASIA CORPORATION) of a main component urethane acrylate, 0.02 parts by mass of Irgacure 184 (manufactured by Chiba Japan) 15 parts by weight of a mixed solution, applied by a bar coater, and dried for 5 minutes at 70 ℃, exposed by an exposure amount of 500mJ / cm ^2, to obtain the thickness of the curable resin layer after drying 10㎛ resin laminate 19 .

The evaluation results of the resin laminate 18 and 19 obtained in Example 12 and Comparative Example 7 are shown in Table 3.

Thickness of the curable resin layer (占 퐉) Pencil hardness Formability Evaluation of resistance curl
(mm) Hayes
(%) Example 12 12 7H ○ ○ 1.5 0.39 Comparative Example 7 12 6H × △ 9.5 0.35

From the results in Table 3, it is suggested that the structure of the present resin laminate can be applied to thermoformability applications. It is presumed that a resin laminate having a low hardness and a high hardness capable of being formed can be formed by adjusting the thickness ratio of the acrylic resin layer and the curable resin layer.

11, 15: This resin laminate
12: resin substrate
13: Acrylic resin layer
14: Curable resin layer

Claims (12)

A curable resin composition comprising an organic-inorganic hybrid hard coating agent on both sides or one side of a resin laminate in which an acrylic resin layer (A) containing 50% by mass or more of an acrylic resin is laminated on both sides or one side of the resin substrate (C) Wherein the acrylic resin layer (A) has a structure in which a thermosetting resin and a thermosetting resin are laminated in the acrylic resin layer matrix, (A) having a pencil hardness of 3H or more comprising or dispersing a hard dispersed phase material obtained by combining a thermosetting resin having an unsaturated bond and an unsaturated bond, wherein the organic-inorganic hybrid hard coating is obtained by copolymerizing and crosslinking with a radical polymerizable monomer (B), and an inorganic component having a reactive functional group to be bonded to the curable resin layer And the surface hardness of the surface on which the curable resin layer (B) is laminated is 7H or more in pencil hardness. delete The method according to claim 1,
Wherein the resin substrate (C) is at least one selected from the group consisting of polycarbonate (PC) resin, triacetyl cellulose (TAC) resin, polyethylene terephthalate (PET) resin, polymethyl methacrylate (PMMA) resin, methyl methacrylate- MS) resin, a polysulfone resin, a norbornene resin, and a cycloolefin resin. The method according to claim 1 or 3,
Wherein the inorganic component having a reactive functional group is ultraviolet reactive silica. The method according to claim 1 or 3,
Wherein the inorganic component in the organic-inorganic hybrid hard coating agent is 10 mass% or more and less than 50 mass%. The method according to claim 1 or 3,
Wherein the curable resin layer (B) comprises a leveling agent having a reactive functional group at an end thereof. The method according to claim 6,
Wherein the leveling agent is a polyether-modified polydimethylsiloxane having an acrylic group or a polyester-modified polydimethylsiloxane having an acrylic group. The method according to claim 1 or 3,
Wherein the curable resin layer (B) comprises a lubricant. A front cover member of a display having the scratch-resistant resin laminate according to any one of claims 1 to 3. A front cover member of a display having the scratch-resistant resin laminate according to claim 4. An image display apparatus comprising the front cover member of the display according to claim 9. An image display apparatus comprising a front cover member of a display according to claim 10.

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