TWI534009B - Forming body, material for front cover of display, and image display device - Google Patents

Description

Shaped body, display front cover material and image display device

The present invention relates to a scratch-resistant resin laminate, which can be preferably used as a surface protection panel disposed on the front side (viewing side) of an image display device, particularly a mobile phone having a touch panel function or LCD sheet, etc. before the cover material.

Conventionally, in the field of cover materials for displays for electronic devices, glass has been widely used from the viewpoint of hardness, heat resistance, and transparency.

However, glass is easily broken by impact and the weight of the glass itself is heavier, so it is being studied to replace it with plastic.

In addition, in recent years, various electronic devices and devices have been reduced in size, weight, performance, and cost, and the use conditions of resin molded products including display covers have become stricter, in order to cope with lower prices or a small amount/multiple For the production of varieties, resin sheets with excellent punching workability and high productivity are strongly required.

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

However, acrylic resins have very brittle properties, so that the processing method is usually carried out by cutting, and is not highly productive.

Further, when using an acrylic resin, for example, compared with steel wool or the like When the hard material is in contact, there is a problem that the matrix resin portion is easily scratched due to the low scratch resistance.

For example, Patent Document 1 proposes a polycarbonate resin laminated sheet for punching, which is laminated on both sides or a single surface of a resin sheet containing a resin material containing a polycarbonate resin as a main component. An acrylic resin layer having an acrylic resin as a main component and having a thickness of 10 to 40 μm is laminated on the acrylic resin layer to have a total thickness of 0.2 to 2.0 mm. This resin laminated sheet has a property of high productivity and excellent scratch resistance due to excellent punching workability.

Further, Patent Document 2 proposes a laminate comprising a polycarbonate resin, which is controlled by a thickness of a layer containing an acrylic resin constituting a laminate containing a polycarbonate resin and a total thickness of the laminate. In the range of the acrylic resin-containing layer or the acrylic resin-containing layer and the polycarbonate resin-containing substrate, the surface hardness, particularly the pencil hardness and impact resistance, is balanced. And suitable for LCD monitor cover.

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

Further, Patent Document 3 proposes a scratch-resistant resin laminate which is laminated with a scratch-resistant resin having a thickness of 1 to 5 μm on a substrate containing an acrylic resin as a thermoplastic matrix resin containing a rigid dispersed phase. Floor. The scratch-resistant resin laminate has a property that even if the base material composed of the acrylic resin is different from the resin material, there is no possibility that warpage, unevenness, peeling, or the like may occur due to curing or shrinkage of the resin.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-049623

[Patent Document 2] International Publication No. WO2008/047940

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-296711

In the resin laminated body disclosed in the above-mentioned Patent Documents 1 and 2, when a structure in which a hard coat layer is laminated on a base material made of an acrylic resin or the like is formed, warpage or shrinkage occurs due to hardening or shrinkage of the resin. Problems such as unevenness and peeling.

Moreover, the scratch-resistant resin disclosed in the above-mentioned Patent Document 3 has a configuration in which a hard resin obtained by radical polymerization is contained as a dispersed phase in a thermoplastic resin which is a matrix resin.

The scratch resistance improves the scratch resistance of the resin molded body, but there is still room for improvement from the viewpoint of surface hardness such as pencil hardness.

Accordingly, it is an object of the present invention to provide a scratch-resistant resin laminate which eliminates the problem of warpage or unevenness and which has a scratch resistance function as a high surface hardness.

The present invention provides a scratch-resistant resin laminate which is characterized in that it has an organic/inorganic hybrid system layer on both sides or a single surface of an acrylic resin layer (A) containing an acrylic resin as a main component. A curable resin layer (B) of a coating agent.

Further, the present invention provides a scratch-resistant resin laminate, which is characterized in that it has a structure in which an acrylic resin is laminated on both sides or a single surface of a resin substrate (C). A resin laminated body is formed as the acrylic resin layer (A) as a main component, and a curable resin layer (B) containing an organic/inorganic hybrid hard coating agent is laminated on at least one surface of the resin laminated body.

The scratch-resistant resin laminate provided by the present invention can eliminate the problem of warpage or unevenness by having a curable resin layer (B) containing an organic/inorganic hybrid hard coating agent, and has resistance as a high surface hardness. Scratch function.

In addition, it is more preferable to use a curable resin layer (B) containing an organic/inorganic hybrid hard coating agent in a resin laminated body having a specific structure to impart excellent punching workability and to have a higher surface hardness. Its scratch resistance.

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

11, 15‧‧‧ This resin laminate

12‧‧‧Resin substrate

13‧‧‧Acrylic resin layer

14‧‧‧ hardened resin layer

Fig. 1 (a) and (b) are views showing an example of a scratch-resistant resin laminate according to the present embodiment.

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

<This resin laminate>

The resin laminated body has a structure in which a curable resin layer (B) containing an organic/inorganic hybrid hard coating agent is laminated on both surfaces or one surface of the acrylic resin layer (A) containing an acrylic resin as a main component. .

Moreover, it is more preferable that the resin laminated body has the following structure: in the resin substrate (C) An acrylic resin layer (A) containing an acrylic resin as a main component is laminated on both sides or a single surface to form a resin laminate, and at least one surface of the resin laminate is laminated with an organic/inorganic hybrid hard coat layer. The curable resin layer (B) of the agent.

<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, and isobutyl (meth)acrylate. , tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate , (meth)acrylic acid propyl acrylate, (meth) hydroxypropyl acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (methyl) Cyclohexyl acrylate, (meth) acrylate Ester, (meth)acrylic acid Ester, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (methyl) Acrylic acrylate, 2-hydroxyethyl (meth) acrylate, 2-(methyl) propylene methoxyethyl succinate, 2-(methyl) propylene methoxyethyl maleate, hydrazine 2-(Methyl) propylene methoxyethyl ester, 2-(methyl) propylene methoxyethyl hexahydrophthalate, pentamethyl (meth) acrylate, (meth) acrylate Apiperidine ester, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and the like.

These may be used alone or in combination of two or more kinds. Moreover, as another monomer which can be polymerized with these acrylic monomers, a polyolefin type monomer, a vinyl type monomer, etc. are mentioned, for example.

The acrylic resin layer (A) preferably contains a hard resin layer (a) having a pencil hardness of 3H or more. Forming an acrylic resin by using a high surface hardness as described above The layer (A) has the advantage of imparting an extremely high surface hardness to the resin laminate.

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

As a preferable method of setting the pencil hardness of the acrylic resin layer (A) to 3H or more, a hard dispersion phase is included in the acrylic resin matrix of the acrylic resin layer (A).

More specifically, a method of forming acrylic acid by a hard resin layer (a) obtained by dispersing/dispersing a hard disperse phase material having excellent heat resistance and scratch resistance in an acrylic resin is used. Resin layer (A).

Examples of the hard dispersed phase material include thermosetting resins, specifically, phenol resins, amine based resins, epoxy resins, polyoxyxylene resins, thermosetting polyimine resins, and thermosetting polyamines. Examples of the polycondensation or addition condensation resin such as an ethyl urethane resin include a thermosetting acrylic resin, a vinyl ester resin, an unsaturated polyester resin, and a diallyl phthalate resin. Addition of a polymerization resin. However, it is not limited to these. The thermosetting resin can be used singly or in combination of two or more. Further, a thermoplastic resin having an unsaturated bond which can be crosslinked with the thermosetting resin can be used in combination.

The shape of the hard dispersed phase is, for example, a particulate form, a spherical shape, a linear form, or a fibrous form, and is preferably spherical in terms of being easily dispersed uniformly in an acrylic resin which is a thermoplastic matrix resin. However, it is not limited to this.

The particle size of the hard dispersed phase is appropriately set depending on the purpose of use, use, and the like of the resin laminate, but is preferably 0.1 to 1000 μm. The blending amount of the hard disperse phase in the acrylic resin layer (A) is appropriately set depending on the purpose of use, use, and the like of the resin laminate, but is preferably 0.1 to 60% by weight.

The method of including the hard dispersed phase in the acrylic resin layer (A) is not particularly limited, and examples thereof include the following methods.

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

b) Then, melt-kneading is carried out, and after forming into a predetermined shape, phase separation and crosslinking are caused, whereby a hard dispersed phase can be formed. In addition, the thermosetting resin may be previously molded into a particulate form or the like, added to the acrylic resin, and kneaded and molded at a temperature at which the thermosetting resin is not melted.

(thickness of acrylic resin layer (A))

The thickness of the acrylic resin layer (A) is preferably 40 μm or more. When the layer thickness of the acrylic resin layer (A) is 40 μm or more, the effect of improving the scratch resistance obtained by 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 μm or more. Moreover, the thickness of the acrylic resin layer (A) is preferably 200 μm or less, and more preferably 100 μm or less from the viewpoint of moldability.

<Curable resin layer (B)>

This resin laminated body has a curable resin layer (B). The curable resin layer (B) is a layer containing an organic/inorganic hybrid hard coating agent, and is responsible for imparting high scratch resistance to the resin laminate without causing warpage or unevenness.

The curable resin layer (B) can be formed, for example, by laminating a coating film on another layer using a coating material containing an organic/inorganic hybrid hard coating agent. However, it is not limited to this method.

As a method of laminating with other layers, a known method is used. For example, a lamination method using a cover film, a dip coating method, a natural coating method, a reverse coating method, Kama coating method, roll coating method, spin coating method, wire bar coating method, extrusion coating method, curtain coating method, spray coating method, gravure coating method, and the like. In addition, for example, a transfer sheet obtained by adhering a curable resin layer (B) to a release layer may be used, and the curable resin layer (B) may be laminated on another layer.

(organic/inorganic hybrid coating agent)

The organic/inorganic hybrid coating agent is composed of a curable resin composition containing an inorganic component having a reactive functional group.

Such an organic/inorganic hybrid coating agent utilizes an inorganic component having a reactive functional group, for example, the inorganic component is copolymerized and crosslinked with a radical polymerizable monomer, whereby the inorganic component is contained in an organic bond. In the organic/inorganic composite coating agent formed by the agent, hardening shrinkage is hard to occur, and the scratch resistance is high.

From the viewpoint of hardening shrinkage, an organic/inorganic hybrid coating agent containing ultraviolet-ray reactive cerium oxide as an inorganic component having a reactive functional group is more preferable.

Further, an organic/inorganic hybrid coating agent containing a UV-reactive phthalic acid gel is preferably used.

Further, examples of the radical polymerizable monomer include polyfunctional (meth)acrylates. For example, examples of the bifunctional (meth) acrylate include ethylene oxide modified diacrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol II ( Methyl) acrylate, 1,9-nonanediol di(meth) acrylate, bisphenol A ethylene oxide modified diacrylate, dimethylol tricyclodecane di(meth) acrylate, Tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, epoxy di(meth)acrylate, ethyl bis(meth)acrylate, and the like.

Moreover, as a trifunctional or more polyfunctional (meth)acrylate, the following are mentioned: Pentaerythritol hexaacrylate, di-trimethylolpropane tetraacrylate, pentaerythritol ethoxy tetraacrylate, trimethylolpropane tri(meth) acrylate or trimethylolpropane triethoxy (methyl) Acrylate, ethyl urethane methacrylate, ethyl urethane tetra(meth) acrylate, ethyl urethane hexacarboxylate, polyester tetra(meth) acrylate, poly Ester hexa(meth) acrylate and the like.

Further, an appropriate one-functional (meth) acrylate can be added for the adjustment of the curing shrinkage ratio and the viscosity in the hard coating, and the solubility of a small amount of the additive. Examples of the monofunctional (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, tert-butyl (meth)acrylate, and (meth)acrylic acid. Ester, octyl (meth) acrylate, isodecyl (meth) acrylate, methoxy polyethylene (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Phenyloxyethyl (meth)acrylate or the like.

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 due to surface hardness, transparency, and punching property. More preferably, it is 10 mass% or more and less than 50 mass%, and it is preferable that it is 15 weight% or more and less than 50 weight%.

(surface adjustment component)

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

The leveling agent may, for example, be a polyfluorene-based leveling agent or an acrylic leveling agent, and particularly preferably a functional group having a reactive terminal at the terminal, and more preferably a functional group having a reactivity of two or more functional groups. .

Specifically, a polyether-modified polydimethyl siloxane having an acryl fluorenyl group having a double bond at both terminals (for example, "BYK-UV 3500" manufactured by BYK-Chemie Japan Co., Ltd.," BYK-UV 3530"), or polyester modified polydimethyl methoxy oxane with 2 propylene groups based on 2 terminals each having 4 double bonds ("BYK-UV 3570" manufactured by BYK-Chemie Japan Co., Ltd.) and the like.

Among these, a polyester-modified polydimethyl siloxane having an acryl oxime group which is stable in haze value and contributes to improvement in scratch resistance is particularly preferable.

(other ingredients)

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

Examples of the lubricant include an anthraquinone compound, a fluorine compound, and a mixed compound thereof. The slidability can be improved by adding these.

In addition to the above, the curable resin layer (B) may be added with, for example, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent or the like as needed.

(thickness of the curable resin layer (B))

The thickness of the curable resin layer (B) is preferably in the range of 5 to 15 μm. When the thickness is 5 μm 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 μm or less, the curable resin layer (B) is not formed. Curing or shrinkage of an ultraviolet curable resin or the like causes warpage, unevenness, peeling, and the like. Further, there is no possibility that the transparency is significantly impaired by the ultraviolet curable resin layer.

The resin laminate has a synergistic effect of the acrylic resin layer (A) having a hard dispersed phase and the curable resin layer (B), and a high hardness can be achieved even in a thin resin laminate. For example, when the thickness of the acrylic resin layer (A) is 200 μm which is the upper limit of the above preferred range, when the thickness of the curable resin layer (B) is less than 5 μm, the resin laminate is used. Unable to achieve high hardness. In contrast, when the thickness of the acrylic resin layer (A) is 40 μm which is the lower limit of the above preferred range, when the thickness of the curable resin layer (B) exceeds 15 μm, the resin laminate is produced. Warped or uneven. As described above, in the present resin laminate, The thickness of the acrylic resin layer (A) is preferably 50 μm or more and 200 μm or less, and the thickness of the curable resin layer (B) is 5 μm or more and 15 μm or less.

In general, it is known that a curable resin layer shrinks when it is hardened, and when it is laminated with other layers, curling tends to occur. The ratio of shrinkage of the curable resin layer tends to be proportional to the thickness of the curable resin layer. Therefore, from the viewpoint of curling, it is not practical to achieve high hardness only by the thickness of the curable resin layer. The curl accompanying the hardening shrinkage of the resin laminate is preferably 3 mm or less, and more preferably 2 mm or less. Moreover, from the viewpoint of suppressing the curl, the thickness ratio of the acrylic resin layer (A) and the curable resin layer (B) is preferably within the above-described range.

<Resin substrate (C)>

The resin substrate (C) is a layer that serves the task of imparting punching workability to the resin laminate. From this point of view, the resin substrate (C) is preferably formed of a resin composition containing a polycarbonate (PC) resin, a cellulose triacetate (TAC) resin, and polyethylene terephthalate. Ester (PET) resin, polymethyl methacrylate (PMMA) resin, methyl methacrylate-styrene copolymerization (MS) resin, polyfluorene resin, drop Any one or more of an olefin resin and a cycloolefin resin.

In a preferred use of the resin laminate, the resin substrate (C) preferably contains a transparent resin.

In the above, the resin substrate (C) is particularly preferably formed of a polycarbonate resin from the viewpoints 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 or a small amount of a polyhydroxy compound is reacted with phosgene.

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

Further, other bisphenol A can be produced by a transesterification method, a pyridine method or the like as a raw material.

Further, a polyester carbonate obtained by a copolymer of bisphenol A and a dicarboxylic acid derivative, for example, p-isophthalic acid dichloride or the like; a derivative of bisphenol A, For example, a polymerization of tetramethyl bisphenol A or the like is obtained.

The molecular weight of the polycarbonate resin is preferably a molecular weight which is a viscosity at which a sheet can be produced by usual extrusion molding, and specifically has a viscosity average molecular weight of 15,000 to 40,000, preferably 20,000 to 35,000. More preferably 22000~30000.

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

<Composition of the resin laminate>

The resin laminated body is required to have an acrylic resin layer (A) and a curable resin layer (B) containing an organic/inorganic hybrid coating agent. Further, it is preferable to further include a resin substrate (C).

More specifically, (B) / (A), (B) / (A) / (B), (B) / (A) / (C), (B) / (A) / ( C)/(B), (B)/(C)/(A)/(B), (B)/(A)/(C)/(A) and (B)/(A)/(C) /(A)/(B), etc. In the above configuration, the curable resin layer (B) is preferably formed on both surfaces of the acrylic resin (A) or in the single-layer layer, and is preferably (B)/(A)/(C) and (B). ) / (A) / (C) / (B).

Fig. 1 is a view showing a configuration of an embodiment of the resin laminate, and Fig. 1(a) illustrates a scratch-resistant resin laminate 15 having a configuration of a single-layer layer of the resin substrate 12. On one side of the resin laminate having the acrylic resin layer 13, a curable resin layer 14 is laminated.

According to this configuration, the synergistic effect of the acrylic resin layer 13 and the curable resin layer 14 has the advantage that the surface can be expressed even when the thickness of the curable resin layer is 5 to 15 μm. Hardness, etc.

In addition, the scratch-resistant resin laminate 11 is exemplified in the resin laminate 12 having the acrylic resin layer 13 on the single-layer layer of the resin substrate 12, and the laminate is laminated. The curable resin layer 14. According to this configuration, since the curable resin layer 14 is also laminated on the resin base material 12, it is possible to suppress the occurrence of process damage on the resin base material 12. Further, the curable resin layer on the side of the resin substrate 12 formed to suppress the occurrence of process damage may be formed of a usual hard coat layer.

<Manufacturing method>

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

The apparatus for producing the resin laminated body includes, for example, a main extruder for extruding a polycarbonate resin and a secondary extruder for extruding an acrylic resin constituting the acrylic resin layer. Usually, the secondary extruder is smaller than the primary extruder.

The temperature of the main extruder is usually 230 to 290 ° C, preferably 240 to 280 ° C, and the temperature of the sub-extruder is usually 220 to 270 ° C, preferably 230 to 260 ° C. Further, in order to remove foreign matter in the resin, it is preferred to provide a polymer filter on the upstream side of the T-die of the extruder.

As a method of depositing two kinds of molten resins by co-extrusion, a known method such as a feeder stage method or a multi-manifold method can be used. In this case, the molten resin laminated in the feeder stage is introduced into a sheet forming mold such as a T-shaped mold, and formed into a sheet shape, and then flows into a mirror-formed forming roll (metal elastic roll or polishing roll) to form a resin accumulation portion. .

The sheet-shaped formed object is mirror-polished and cooled during the forming roll. Laminated body.

Further, in the case of a multi-manifold mold, the molten resin laminated in the mold is similarly formed into a sheet shape in the mold, and then surface-polished and cooled by a forming roll to form a laminate. The temperature of the mold is usually 210 to 300 ° C, preferably 230 to 280 ° C, and the forming roll temperature is usually 100 to 190 ° C, preferably 110 to 180 ° C. A vertical roll or a horizontal roll can be suitably used for a roll.

<Use>

The resin laminate is useful as a surface protection panel that is disposed on the front side (viewing side) of the image display device, in particular, a front cover material such as a mobile phone or a liquid crystal tablet having a touch panel function.

<Description of terms>

Generally, the term "film" refers to a thin and flat product which is extremely small in thickness and has a maximum thickness, and is usually supplied in the form of a roll (Japanese Industrial Standard JISK6900); usually called "sheet" , refers to an article that is thin and generally has a thickness that is smaller and flatter than the length and width, based on the definition in JIS. However, the boundary between the sheet and the film is not clear, and it is not necessary to distinguish between the two in the present invention. Therefore, in the present invention, the case called "film" also includes "sheet", which is called " The case of "sheet" also includes "film".

In addition, in the case where it is expressed as "main component" in the present specification, unless otherwise specified, it means that other components are allowed to be contained within a range that does not hinder the function of the main component.

In this case, the content of the main component is not particularly limited, but the main component (in the case of two or more components as the main component, the total amount of the components) is 50% by mass or more, preferably 70%. More than or equal to the mass%, particularly preferably 90% by mass or more (including 100%).

In the present invention, when it is expressed as "X~Y" (X, Y is an arbitrary number), unless otherwise specified, "X or more and Y or less" is included, and "better than X" and "preferably less than Y" mean.

Further, in the present invention, when it is expressed as "X or more" (X is an arbitrary number), unless otherwise specified, "the meaning is preferably greater than X", and the expression is "Y or less". In the case of (Y is an arbitrary number), "it is preferable to be smaller than Y" unless otherwise specified.

[Examples]

The present invention will be described in more detail below by way of examples, but the invention is not limited thereto, and various applications can be made without departing from the scope of the invention.

<Measurement and evaluation method>

First, the measurement methods and evaluation methods of various physical property values of the samples obtained in the examples and the comparative examples will be described.

(surface hardness evaluation)

With respect to the resin laminates of the examples and the comparative examples, the pencil hardness of the surface was measured in accordance with JIS K 5600-5-4.

(scratch resistance evaluation)

For the resin laminates of the examples and the comparative examples, the surface of the resin laminate (the side of the curable resin layer) was rubbed back and forth 50 times with a weight of 1000 g using steel wool of #0000 to visually observe the presence or absence of damage. In addition, in Table 1, ○ means "no damage", △ means "there is damage, but it is a practical level", and × means "damage".

<Punchability>

20 cm square test sample of the resin laminate of the examples and the comparative examples, A punching test was carried out using a dumbbell knife of JIS K 6251 and a screw press manufactured by Toyo Seiki Co., Ltd. The evaluation was based on whether or not cracks were present on the perforated sample piece and the substrate, or whether or not the substrate was broken. ○ indicates "no crack or crack", and × indicates "rupture or cracking".

<Curl Test>

A cured film layer was formed in the same manner as in the methods described in the respective examples and comparative examples using a PET film of A4 size (manufactured by Mitsubishi Plastics, trade name "DIAFOIL") of 125 μm as a resin substrate. The central portion of each sample was cut into 10 cm squares as test samples. The evaluation system measures the warpage of the four corners using a gauge, and the average value of the four points is used as the curl value of the test sample.

<Example 1>

In the extrusion molding machine, the polycarbonate resin (Mitsubishi Engineering-Plastics) containing the base resin is used so that the thickness of the base resin layer is 560 μm, the thickness of the acrylic resin layer is 140 μm, and the thickness of the laminate is 700 μm. A layer of a mixture of 80 parts by mass and 20 parts by mass of PCTG (manufactured by SK CHEMICAL Co., Ltd., trade name "SKYGREEN J2003"), and an acrylic resin containing a hard dispersed phase (Arkema Co., Ltd., manufactured under the trade name "Iupilon S1000") The layer of the product name "Altuglas HT121" was produced by co-extrusion into a layered product a. The extrusion conditions were such that the extrusion temperature of the acrylic resin layer was 240 ° C, the extrusion temperature of the base resin layer was 265 ° C, the roll temperature was R1 = 110 ° C, R2 = 120 ° C, and R3 = 125 ° C.

An organic/inorganic hybrid ultraviolet curable hard coating agent (manufactured by DIC Corporation, trade name "EKS1105") having an ultraviolet reactive functional group is applied to the surface of the acrylic resin layer of the laminate a by a bar coater. Inorganic component (ceria oxide) content: 15 to 25% by mass) 10 parts by mass, Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) 0.2 parts by mass, and MEK 2 parts by mass, mixed at 70 ° C for 3 minutes, and then 500 mJ The exposure amount of /cm ² was exposed to obtain a resin laminate 1 having a thickness of the curable resin layer after drying of 5 μm.

<Example 2>

An organic/inorganic hybrid ultraviolet curable hard coat agent (manufactured by Momentive Co., Ltd., trade name "UVHC7800", which has ultraviolet reactive functional groups, is applied to the surface of the acrylic resin layer of the laminate a using a bar coater. Inorganic component (cerium oxide) content: 40 to 50% by mass), after drying at 90 ° C for 1 minute, exposure is carried out at an exposure amount of 500 mJ/cm ^{2 to} obtain a resin having a thickness of 6 μm after drying of the curable resin layer. Laminated body 2.

<Example 3>

A polyester modified polydimethyl siloxane having an acrylonitrile group (manufactured by BYK-Chemie Japan Co., Ltd., trade name "BYK-UV3570") was added as a blend with respect to 100 parts of the hard coating agent in a ratio of 5 parts. In the same manner as in Example 2, a resin laminate 3 having a thickness of the cured resin layer after drying of 6 μm was obtained in the same manner as in Example 2.

<Example 4>

An organic/inorganic hybrid ultraviolet curable hard coating agent (product name "EXCERATE RUA-069VE", manufactured by Asia Minor Industries Co., Ltd., having an ultraviolet reaction, is applied to the surface of the acrylic resin layer of the laminate a by a bar coater. The content of the inorganic component (cerium oxide) of the functional group is 5 to 15% by mass, and after drying at 90 ° C for 1 minute, exposure is performed at an exposure amount of 500 mJ/cm ^{2 to} obtain the thickness of the cured resin layer after drying. It is a resin laminated body 4 of 6 μm.

<Example 5>

An organic/inorganic hybrid ultraviolet curable hard coating agent (manufactured by Momentive Co., Ltd., trade name "UVHC7300", which has ultraviolet reactive functional groups, is applied to the surface of the acrylic resin layer of the laminate a by a bar coater. Inorganic component (cerium oxide) content: 10 to 20% by mass), after drying at 90 ° C for 1 minute, exposure was carried out at an exposure amount of 500 mJ/cm ^{2 to} obtain a resin having a thickness of 6 μm after drying of the curable resin layer. Laminated body 5.

<Example 6>

An acrylic resin (manufactured by Arkema Co., Ltd., trade name "Altuglas HT121") having a hard dispersed phase was molded into a laminate b containing an acrylic resin layer having a thickness of 700 μm by an extrusion molding machine. The extrusion conditions were as follows: extrusion temperature was 240 ° C, roll temperature was R1 = 1010 ° C, R2 = 120 ° C, and R3 = 125 ° C.

An organic/inorganic hybrid ultraviolet curable hard coating agent (manufactured by Momentive Co., Ltd., trade name "UVHC7800", an inorganic component having ultraviolet reactive functional groups (two) is applied to one surface of the laminated body b by a bar coater. silicon oxide) content: after 40 to 50 mass%), dried at 90 ℃ 1 minute exposure dose 500mJ / cm ² of exposed, to obtain a thickness of resin layer after drying was 6μm of the resin laminate 6.

<Comparative Example 1>

An ultraviolet curable hard coat agent whose main component is ethyl urethane acrylate is applied to the surface of the acrylic resin layer of the laminate a using a bar coater (product name "EXCERATE RUA-066VE", manufactured by Asia Minor Industries, Ltd. ” 10 parts by mass, a mixed solution of 0.02 parts by mass of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) and 15 parts by mass of MEK, at 70. After drying at ° C for 5 minutes, the film was exposed to an exposure amount of 500 mJ/cm ^{2 to} obtain a resin laminate 7 having a thickness of the cured resin layer after drying of 7 μm.

<Comparative Example 2>

An ultraviolet curable hard coat agent (manufactured by Momentive Co., Ltd., trade name "UVHC1101") whose main component is urethane urethane is applied to the surface of the acrylic resin layer of the laminate a by a bar coater. After drying at 90 ° C for 1 minute, the film was exposed to an exposure amount of 500 mJ/cm ^{2 to} obtain a resin laminate 8 having a thickness of the cured resin layer after drying of 8 μm.

<Comparative Example 3>

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

An organic/inorganic hybrid ultraviolet curable hard coating agent (manufactured by Momentive Co., Ltd., trade name "UVHC7800", an inorganic component having an ultraviolet reactive functional group) is applied to one surface of the resin sheet c by a bar coater. Cerium dioxide content: 40 to 50% by mass), after drying at 90 ° C for 1 minute, exposure is carried out at an exposure amount of 500 mJ/cm ^{2 to} obtain a resin laminate 9 having a thickness of the cured resin layer after drying of 6 μm. .

<Comparative Example 4>

A single-layer resin sheet d having a thickness of 700 μm was formed by an extrusion molding machine using an acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name "ACRYPET VH001") having a hard dispersed phase. The extrusion conditions were: extrusion temperature of 240 ° C, roll temperature of R1 = 100 ° C, R2 = 110 ° C, and R3 = 125 ° C.

An ultraviolet curable hard coat agent (manufactured by Asiac Industrial Co., Ltd., trade name "EXCERATE RUA-066VE") whose main component is urethane urethane is applied to one surface of the resin sheet d using a bar coater. After drying at 70 ° C for 5 minutes, the film was exposed to an exposure amount of 500 mJ/cm ^{2 to} obtain a resin laminated body 10 having a thickness of the dried curable resin layer of 6 μm.

The evaluation results of the resin laminates 1 to 10 obtained in Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Table 1. For the overall evaluation, the pencil hardness was 7H or more, and the value of the crimp test was 2 mm or less as ○, and the one not satisfied was recorded as ×.

According to the results of Table 1, in the urethane-based urethane-based ultraviolet curable hard coating agent of Comparative Example 1 and Comparative Example 2, the pencil hardness was 7H, but the amount of curl was large, which was not practical.

On the other hand, in the examples using the organic/inorganic hybrid ultraviolet curable hard coating agent, the pencil hardness was high, and no warpage or unevenness was observed.

In particular, in the organic/inorganic hybrid ultraviolet curable hard coating agents of Examples 1 to 3 and Example 6, a pencil hardness of 8H was achieved.

However, in Comparative Example 3, although an organic/inorganic hybrid ultraviolet curable hard coat agent was used for the polycarbonate resin, the hardness of the base resin was low, so that sufficient pencil hardness was not obtained.

According to these results, it is possible to obtain a higher hardness and scratch resistance by laminating a layer of a curable resin containing an organic/inorganic hybrid hard coating agent on a laminate of an acrylic resin. Resin laminate.

Further, in the present examples and comparative examples, in order to make the difference in the curl test more clear, a PET film was used, and it was estimated that the same tendency was observed in the laminated bodies 1 to 3.

<Curl Test 2>

Using the laminate d described below as a resin substrate, a cured resin layer was formed in the same manner as in the methods described in the respective examples and comparative examples. The central portion of each sample was cut into 10 cm squares as test samples. The evaluation system measures the warpage of the four corners using a gauge, and the average value of the four points is used as the curl value in the test sample. Further, the crimp value also includes the value of the thermal expansion portion of the original sheet.

<Haze>

The test sample of 5 cm square of the resin laminate of the examples and the comparative examples was measured using NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) as a test machine. The test was carried out in accordance with JIS K 7136, and the average value thereof was taken as the haze value of the test sample.

<Example 7>

In the extrusion molding machine, a polycarbonate resin (available from SSPC Co., Ltd.) is used as a base resin, so that the thickness of the base resin layer is 240 μm, the thickness of the acrylic resin layer is 60 μm, and the thickness of the laminate is 300 μm. Product name "CALIBRE301-4") A layer of a mixture of 80 parts by mass and 20 parts by mass of PCTG (manufactured by SK CHEMICAL Co., Ltd., trade name "SKYGREEN J2003"), and an acrylic resin (available from Arkema Co., Ltd.) having a hard dispersed phase. The layer of the trade name "Altuglas HT121" is formed into a laminate d by co-extrusion. The extrusion conditions were such that the extrusion temperature of the acrylic resin layer was 240 ° C, the extrusion temperature of the base resin layer was 265 ° C, the roll temperature was R1 = 110 ° C, R2 = 115 ° C, and R3 = 95 ° C.

An organic/inorganic hybrid ultraviolet curable hard coating agent (manufactured by DIC Corporation, trade name "EKS1105") having an ultraviolet reactive functional group is applied to the surface of the acrylic resin layer of the laminate d by a bar coater. Inorganic component (ceria oxide) content: 15 to 25% by mass) 10 parts by mass, 0.2 parts by mass of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.), and 2 parts by mass of MEK, dried at 70 ° C for 3 minutes, and then 500 mJ The exposure amount of /cm ² was exposed to obtain a resin laminate 11 having a thickness of the cured resin layer after drying of 12 μm.

<Example 8>

An organic/inorganic hybrid ultraviolet curable hard coat agent (manufactured by Momentive Co., Ltd., trade name "UVHC7800", which has ultraviolet reactive functional groups, is applied to the surface of the acrylic resin layer of the laminate d using a bar coater. Inorganic component (cerium oxide) content: 40 to 50% by mass), after drying at 90 ° C for 1 minute, exposure is carried out at an exposure amount of 500 mJ/cm ^{2 to} obtain a resin having a thickness of the cured resin layer of 12 μm after drying. Laminated body 12.

<Example 9>

A polyester modified polydimethyl siloxane having an acrylonitrile group (manufactured by BYK-Chemie Japan Co., Ltd., trade name "BYK-UV3570") was added as a blend with respect to 100 parts of the hard coating agent in a ratio of 5 parts. In the same manner as in Example 2, a resin laminate 13 having a thickness of the cured resin layer after drying of 12 μm was obtained in the same manner as in Example 2.

<Example 10>

An organic/inorganic hybrid ultraviolet curable hard coat agent (product name "EXCERATE RUA-069VE", manufactured by Asia Minor Industries Co., Ltd., having an ultraviolet reaction, is applied to the surface of the acrylic resin layer of the laminate d using a bar coater. The content of the inorganic component (cerium oxide) of the functional group is 5 to 15% by mass, and after drying at 90 ° C for 1 minute, exposure is performed at an exposure amount of 500 mJ/cm ^{2 to} obtain the thickness of the cured resin layer after drying. It is a resin laminate 14 of 12 μm.

<Example 11>

An organic/inorganic hybrid ultraviolet curable hard coat agent (manufactured by Momentive Co., Ltd., trade name "UVHC7300", which has ultraviolet reactive functional groups, is applied to the surface of the acrylic resin layer of the laminate d using a bar coater. Inorganic component (cerium oxide) content: 10 to 20% by mass), after drying at 90 ° C for 1 minute, exposure was carried out at an exposure amount of 500 mJ/cm ^{2 to} obtain a resin having a thickness of the cured resin layer of 12 μm after drying. Laminated body 15.

<Comparative Example 5>

An ultraviolet curable hard coat agent whose main component is urethane urethane is applied to the surface of the acrylic resin layer of the laminate d using a bar coater (product name "EXCERATE RUA-066VE", manufactured by Asia Minor Industries, Ltd. ” 10 parts by mass, a mixed solution of 0.02 parts by mass of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) and 15 parts by mass of MEK, dried at 70° C. for 5 minutes, and then exposed to an exposure amount of 500 mJ/cm ^{2 to} obtain a dried image. The resin layered body 16 having a thickness of the curable resin layer of 12 μm.

<Comparative Example 6>

An ultraviolet curable hard coat agent (manufactured by Momentive Co., Ltd., trade name "UVHC1101") whose main component is urethane urethane is applied to the surface of the acrylic resin layer of the laminate d using a bar coater. after drying at 90 deg.] C for 1 minute, an exposure amount of 500mJ / cm ² of the exposure, the thickness of the resin layer is obtained after drying was 12μm of the resin laminate 17.

The resin laminates 11 to 17 obtained in Examples 7 to 11 and Comparative Examples 4 to 5 were used. The evaluation results are shown in Table 2. For the overall evaluation, the pencil hardness was 7H or more, and the value of the crimp test was 2 mm or less as ○, and the one not satisfied was recorded as ×.

From the results of Table 2, it was confirmed that the urethane urethane-based ultraviolet curable hard coating agents of Comparative Example 5 and Comparative Example 6 did not reach the practical level in terms of scratch resistance and curling.

On the other hand, Examples 7 to 11 have almost no curl, and although they are a film substrate of 300 μm, a laminate having a pencil hardness of 8H or more and a high hardness is obtained. In particular, in Examples 7 to 9, the surface hardness of the highest pencil hardness level of 9H was achieved, and in Example 9, a more excellent haze value was obtained by adding a leveling agent.

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

<formability>

The test samples of the A4 size of the resin laminates of Example 12 and Comparative Example 7 were subjected to vacuum forming. The test conditions were: a molding temperature of 110 ° C, a vacuum pressure of 0.1 MPa, a molding time of 10 seconds, a corner of the mold of R = 2 mm, and a depth of stretching of 20 mm. In the evaluation, the sample after molding was visually evaluated, ○ indicates "no crack", and × indicates "rupture".

<Example 12>

In the extrusion molding machine, a polycarbonate resin (base PC resin) (manufactured by SSPC Co., Ltd.) was used, in which the thickness of the base resin layer was 105 μm, the thickness of the acrylic resin layer was 20 μm, and the thickness of the laminate was 125 μm. Product name "CALIBRE301-4") A layer of a mixture of 80 parts by mass and 20 parts by mass of PCTG (manufactured by SK CHEMICAL Co., Ltd., trade name "SKYGREEN J2003"), and an acrylic resin (available from Arkema Co., Ltd.) having a hard dispersed phase. The layer of the trade name "Altuglas HT121" is extruded to form a layered body e. The extrusion conditions were such that the extrusion temperature of the acrylic resin layer was 240 ° C, the extrusion temperature of the base resin layer was 265 ° C, the roll temperature was R1 = 110 ° C, R2 = 110 ° C, and R3 = 80 °C.

An organic/inorganic hybrid ultraviolet curable hard coat agent (manufactured by MOMENTIVE Co., Ltd., trade name "UVHC7800F", which has ultraviolet reactive functional groups, is applied to the surface of the acrylic resin layer of the laminate e by a bar coater. Inorganic component (cerium oxide) content: 30 to 40% by mass), after drying at 90 ° C for 1 minute, exposure is carried out at an exposure amount of 500 mJ/cm ^{2 to} obtain a resin having a thickness of 10 μm after drying of the curable resin layer. Laminated body 18.

<Comparative Example 7>

An ultraviolet curable hard coat agent whose main component is urethane acrylate is applied to the surface of the acrylic resin layer of the laminate e using a bar coater (product name "EXCERATE RUA-066VE", manufactured by Asia Minor Industries, Ltd. ” 10 parts by mass, a mixed solution of 0.02 parts by mass of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) and 15 parts by mass of MEK, dried at 70° C. for 5 minutes, and then exposed to an exposure amount of 500 mJ/cm ^{2 to} obtain a dried image. The resin laminate 19 having a thickness of the curable resin layer of 10 μm.

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

According to the results of Table 3, it is suggested that the constitution of the resin laminate can also be applied to the possibility of thermoformability. It is presumed that a resin laminated body having a low curl and a high hardness which can be formed can be formed by adjusting the ratio of the thickness of the acrylic resin layer and the curable resin layer.

11, 15‧‧‧ This resin laminate

12‧‧‧Resin substrate

13‧‧‧Acrylic resin layer

14‧‧‧ hardened resin layer

Claims (10)

A molded article obtained by thermoforming a scratch-resistant resin laminate, and the scratch-resistant resin laminate system has a configuration in which an acrylic resin is contained on both surfaces of the resin substrate (C) or a single-layer layer. a resin laminate of the acrylic resin layer (A) of the component, wherein a curable resin layer (B) containing an organic/inorganic hybrid hard coating agent is laminated on at least one surface of the resin laminate; the acrylic resin layer ( A) a hard resin layer (a) having a hard disperse phase in an acrylic resin layer matrix, the organic/inorganic hybrid hard coat agent being composed of a curable resin composition containing an inorganic component having a reactive functional group The acrylic resin layer (A) has a thickness of 40 to 200 μm, and the curable resin layer (B) has a thickness of 5 to 15 μm. The molded article of the first aspect of the invention is characterized in that the surface hardness of the surface on which the curable resin layer (B) is laminated is a pencil hardness of 7H or more. The molded article of the first aspect of the invention, wherein the acrylic resin layer (A) is a hard resin layer (a) having a pencil hardness of 3H or more. The molded article of the second aspect of the invention, wherein the acrylic resin layer (A) is a hard resin layer (a) having a pencil hardness of 3H or more. The molded article according to any one of claims 1 to 4, wherein the hard resin layer (a) contains or is dispersed with a hard dispersed phase material, which is composed of two kinds, either alone or in combination. It is obtained by the above thermosetting resin, or by combining a thermosetting resin and a thermoplastic resin having an unsaturated bond crosslinkable with the thermosetting resin. The molded article according to any one of claims 1 to 4, wherein the organic/inorganic hybrid hard coating agent is contained by having a copolymerizable monomer with a radical polymerizable monomer. A curable resin composition of an inorganic component of a reactive functional group which is polymerized and crosslinked. The molded article according to any one of claims 1 to 4, wherein the inorganic component is ultraviolet-reactive cerium oxide. The molded article according to any one of claims 1 to 4, wherein the resin substrate (C) contains a compound selected from the group consisting of polycarbonate (PC) resin, cellulose triacetate (TAC) resin, and polyparaphenylene Ethylene formate (PET) resin, polymethyl methacrylate (PMMA) resin, methyl methacrylate-styrene copolymerization (MS) resin, polyfluorene resin, drop Any one or more of a group of an olefin resin and a cycloolefin resin. A display front cover material having the molded body of any one of claims 1 to 8. An image display device comprising a front cover material for a display of claim 9 of the patent application.