HK1191295B - Abrasion-resistant resin laminate, material for front cover of display and image display device - Google Patents

Description

Scratch-resistant resin laminate, front plate material for display, and image display device

Technical Field

The present invention relates to a scratch-resistant resin laminate which can be suitably used as a front plate material for a surface protection panel, particularly a mobile phone having a touch panel function, a liquid crystal writing pad, and the like, which is disposed on the front surface side (visible side) of an image display device and is used.

Background

In the field of panel materials for displays of electronic devices and the like, glass is widely used from the viewpoint of hardness, heat resistance, and transparency.

However, glass is easily broken by impact and also the glass itself is heavy, and therefore, substitution thereof with plastic is under study.

In addition, recently, miniaturization, weight reduction, high performance, and price reduction of various electronic devices and apparatuses have been advanced, and conditions for using resin molded articles represented by display panels have become more and more strict, and a resin sheet having excellent punching workability and high productivity is demanded in order to meet the demand for cost reduction and small-volume and multi-variety production.

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

However, since acrylic resins have a very brittle property, the processing method thereof is generally performed by cutting, and the productivity is high.

Further, when an acrylic resin is used, for example, when the acrylic resin is brought into contact with a hard material such as steel wool, the scratch resistance of the matrix resin portion is low, and therefore, the acrylic resin is easily damaged.

For example, patent document 1 proposes a polycarbonate resin laminated sheet for punching, which is obtained by laminating acrylic resin layers containing an acrylic resin as a main component, in a thickness of 10 to 40 μm on both surfaces or one surface of a resin sheet made of a resin material containing a polycarbonate resin as a main component, and laminating a hard coat layer on the acrylic resin layers, thereby forming a total thickness of 0.2 to 2.0 mm. The resin laminate sheet has the following properties: has excellent punching workability, and therefore, has high productivity and excellent scratch resistance.

Patent document 2 proposes a polycarbonate resin-containing laminate suitable for a liquid crystal display panel, in which the thickness of an acrylic resin-containing layer constituting the laminate and the total thickness of the laminate are controlled to be within specific ranges, wherein the laminate contains a polycarbonate resin, and a hard coat treatment is performed on the acrylic resin-containing layer or on the acrylic resin-containing layer and a base material containing a polycarbonate resin, so that the surface hardness, particularly pencil hardness and impact resistance are balanced.

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

Patent document 3 proposes a scratch-resistant resin laminate in which a scratch-resistant resin layer having a thickness of 1 to 5 μm is laminated on a substrate made of an acrylic resin as a thermoplastic matrix resin containing a hard dispersed phase. The scratch-resistant resin laminate has the following properties: even if the base material made of acrylic resin is different from the resin material, warpage, bending, peeling, and the like do not occur due to curing and shrinkage of the resin.

Patent document

Patent document 1: japanese laid-open patent publication No. 2008-049623

Patent document 2: international laid-open pamphlet WO2008/047940 publication

Patent document 3: japanese laid-open patent publication No. 2007-296711

Disclosure of Invention

Problems to be solved by the invention

In the resin laminates disclosed in patent documents 1 and 2, when a hard coat layer is laminated on a base material made of an acrylic resin or the like, there is a problem that warpage, bending, peeling, and the like are generated along with curing and shrinkage of the resin.

The scratch-resistant resin disclosed in patent document 3 has the following structure: the thermoplastic resin as the matrix resin contains a hard resin as a dispersed phase obtained by radical polymerization.

The scratch resistance of the resin molded article is improved by the dispersed phase, but there is still room for improvement from the viewpoint of surface hardness such as pencil hardness.

Accordingly, an object of the present invention is to provide a scratch-resistant resin laminate having a scratch-resistant function as high surface hardness while solving the problems of warpage and warpage.

Means for solving the problems

The invention provides a scratch-resistant resin laminate having a structure in which a curable resin layer (B) is laminated on both surfaces or one surface of an acrylic resin layer (A), wherein the acrylic resin layer (A) contains an acrylic resin as a main component, and the curable resin layer (B) contains an organic-inorganic hybrid hard coating agent.

The present invention also provides a scratch-resistant resin laminate having a structure in which a curable resin layer (B) is laminated on at least one surface of a resin laminate, wherein the resin laminate is formed by laminating an acrylic resin layer (a) on both surfaces or one surface of a resin base material (C), the acrylic resin layer (a) contains an acrylic resin as a main component, and the curable resin layer (B) contains an organic-inorganic hybrid hard coating agent.

ADVANTAGEOUS EFFECTS OF INVENTION

The scratch-resistant resin laminate provided by the present invention has a scratch-resistant function as a high surface hardness while eliminating the problems of warpage and warpage by having the curable resin layer (B) containing an organic-inorganic hybrid hard coating agent.

Further, it is more preferable to apply the curable resin layer (B) containing an organic-inorganic hybrid hard coating agent to a resin laminate having a specific structure, thereby providing excellent punching workability and also having a scratch resistance function as a higher surface hardness.

Therefore, the scratch-resistant resin laminate can be suitably used as a front plate material for a liquid crystal display, particularly a front plate material for a mobile phone and a liquid crystal writing pad having a touch panel function.

Drawings

Fig. 1 is a view showing an example of the scratch-resistant resin laminate according to the present embodiment.

Description of the symbols

11. 15: this resin laminate

12: resin base material

13: acrylic resin layer

14: curable resin layer

Detailed Description

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

< present resin laminate >

The resin laminate has a structure in which a curable resin layer (B) is laminated on both surfaces or one surface of an acrylic resin layer (A), wherein the acrylic resin layer (A) contains an acrylic resin as a main component, and the curable resin layer (B) contains an organic-inorganic hybrid hard coating agent. More preferably, the resin laminate has a structure in which a curable resin layer (B) is laminated on at least one side of a resin laminate formed by laminating an acrylic resin layer (a) containing an acrylic resin as a main component on both sides or one side of a resin base material (C), and the curable resin layer (B) contains an organic-inorganic hybrid hard coating 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, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like.

These may be used alone or in combination of 2 or more. Examples of the other monomer polymerizable with these acrylic monomers include polyolefin monomers and vinyl monomers.

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 a substance having a high surface hardness as described above, the present resin laminate can be provided with an advantage such as an extremely high surface hardness.

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

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

More specifically, there may be mentioned: a method for forming an acrylic resin layer (A) by incorporating and dispersing a hard resin layer (a) comprising a hard dispersed phase material having superior heat resistance and scratch resistance to an acrylic resin.

Examples of the hard dispersed phase material include thermosetting resins, and specifically, include: polycondensation or addition-polycondensation resins such as phenol resins, amino resins, epoxy resins, silicone resins, thermosetting polyimide resins, thermosetting polyurethane resins, and the like, and in addition, there may be mentioned: thermosetting acrylic resins, vinyl ester resins, unsaturated polyester resins, diallyl phthalate resins, and other addition polymerization resins. However, the above substances are not limited thereto. The thermosetting resin may be used alone or in combination of 2 or more. In addition, a thermoplastic resin having an unsaturated bond which can be crosslinked with these thermosetting resins may be used in combination.

The shape of the hard dispersed phase may be in the form of particles, spheres, threads, fibers, etc., and spheres are preferred because they are easily and uniformly dispersed in the acrylic resin as the thermoplastic matrix resin. However, the present invention is not limited thereto.

The particle size of the hard dispersed phase can be suitably set according to the purpose and use of the resin laminate, and is preferably 0.1 to 1000 μm. The amount of the hard dispersion phase to be blended in the acrylic resin layer (a) is suitably set in accordance with the purpose of use, application, and the like of the present resin laminate, and is preferably 0.1 to 60% by weight.

The method of containing 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 an acrylic resin material.

b) Then, melt kneading is performed, and after molding into a predetermined shape, phase separation and crosslinking are caused, whereby a hard dispersed phase can be constituted. The thermosetting resin may be molded into particles or the like in advance, added to the acrylic resin, and then kneaded and molded at a temperature at which the thermosetting resin does not melt.

(thickness of acrylic resin layer (A))

The thickness of the acrylic resin layer (A) is preferably 40 μm or more. If the layer thickness of the acrylic resin layer (a) is 40 μm or more, there is no fear that the effect of improving the scratch resistance of the acrylic resin layer cannot be obtained. From this viewpoint, the thickness of the acrylic resin layer (a) is more preferably 50 μm or more. From the viewpoint of moldability, the thickness of the acrylic resin layer (a) is preferably 200 μm or less, and more preferably 100 μm or less.

< curable resin layer (B) >

The resin laminate comprises a curable resin layer (B). The curable resin layer (B) contains an organic-inorganic hybrid hard coating agent, does not cause warpage or warpage, and is a layer that imparts a high scratch resistance to the resin laminate.

The curable resin layer (B) can be formed by, for example, laminating a coating material containing an organic-inorganic hybrid hard coating agent on another layer as a coating film. However, the method is not limited thereto.

As a method of stacking with other layers, a known method can be used. Examples thereof include: a lamination method using a protective film, a dip coating method, a natural coating method, a reverse roll coating method, a comma coating method, a roll coating method, a spin coating method, a wire bar coating method, an extrusion coating method, a curtain coating method, a spray coating method, a gravure coating method, or the like. For example, a method of laminating the curable resin layer (B) on another layer using a transfer sheet in which the curable resin layer (B) is bonded to a release layer may be employed.

(coating agent of organic-inorganic hybrid type)

Examples of the organic-inorganic hybrid coating agent include coating agents 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, and, for example, by copolymerizing and crosslinking the inorganic component with a radical polymerizable monomer, it is possible to exhibit higher abrasion resistance and less likely to cause curing shrinkage than an organic-inorganic hybrid coating agent containing an inorganic component in an organic binder.

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 is more preferable.

Further preferable examples of the coating agent include organic-inorganic hybrid coating agents containing ultraviolet-reactive colloidal silica.

In addition, examples of the radical polymerizable monomer include polyfunctional (meth) acrylates. For example, as the 2-functional (meth) acrylate, there may be mentioned: ethylene oxide-modified diacrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) 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, polyurethane di (meth) acrylate, and the like.

Further, examples of the 3-or more-functional polyfunctional (meth) acrylate include: pentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol ethoxytetraacrylate, trimethylolpropane tri (meth) acrylate and trimethylolpropane triethoxy (meth) acrylate, polyurethane tri (meth) acrylate, polyurethane tetra (meth) acrylate, polyurethane hexaacrylate, polyester tetra (meth) acrylate, polyester hexaacrylate, and the like.

Furthermore, monofunctional (meth) acrylates may be added as appropriate to adjust the curing shrinkage and viscosity of the hard coat layer and to improve the solubility of a small amount of additives. Examples of monofunctional (meth) acrylates include: methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, isobornyl (meth) acrylate, octyl (meth) acrylate, isodecyl (meth) acrylate, methoxy polyethylene (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, and 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, more preferably 10% by mass or more and less than 50% by mass, and most preferably 15% by mass or more and less than 50% by mass, from the viewpoint of surface hardness, transparency, punching processability, and the like.

(surface modifying component)

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

Examples of the leveling agent include a polysiloxane-based leveling agent and an acrylic leveling agent, and a leveling agent having a reactive functional group at an end is particularly preferable, and a leveling agent having a reactive functional group of 2 or more functions is more preferable.

Specifically, there may be mentioned: examples of the polyether-modified polydimethylsiloxane having an acryl group and a double bond at both ends thereof include a polyether-modified polydimethylsiloxane having a double bond at both ends (for example, "BYK-UV 3500" manufactured by BYK-CHEMIE JAPAN and "BYK-UV 3530", and a polyester-modified polydimethylsiloxane having an acryl group and a total of 2 double bonds at each end thereof (for example, "BYK-UV 3570" manufactured by BYK-CHEMIE JAPAN).

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

(other Components)

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

Examples of the lubricant include: a silicon-based compound, a fluorine-based compound, or a mixed compound thereof. Lubricity can be improved by adding these substances.

The curable resin layer (B) may contain, in addition to the above components, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, and the like, as required.

(thickness of 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) can be sufficiently obtained, while when the thickness is 15 μm or less, there is no fear that warpage, bending, peeling, and the like are generated by curing and shrinkage of an ultraviolet curable resin or the like constituting the curable resin layer (B). Further, there is no fear that transparency is significantly impaired by the ultraviolet curable resin layer.

The resin laminate can realize high hardness even in a thin resin laminate by the synergistic effect of the acrylic resin layer (A) containing a hard dispersed phase and the curable resin layer (B). For example, when the thickness of the acrylic resin layer (a) is 200 μm, which is the upper limit of the preferable range, if the thickness of the curable resin layer (B) is less than 5 μm, the present resin laminate cannot achieve high hardness. On the other hand, when the thickness of the acrylic resin layer (a) is 40 μm, which is the lower limit of the above preferable range, if the thickness of the curable resin layer (B) exceeds 15 μm, warpage and warpage may occur in the present resin laminate. As described above, in the present resin laminate, in order to realize high hardness, it is particularly preferable that the thickness of the acrylic resin layer (a) is 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 as the lamination ratio.

It is known that a curable resin layer generally shrinks during curing, and curling is likely to occur when the curable resin layer is laminated with another layer. Since the shrinkage ratio of the curable resin layer tends to be proportional to the thickness of the curable resin layer, it is not practical to achieve high hardness only by the thickness of the curable resin layer from the viewpoint of curling. The curl accompanying the curing shrinkage of the resin laminate is preferably 3mm or less, and more preferably 2mm or less. In addition, from the viewpoint of suppressing curling, it is preferable that the thickness ratio of the acrylic resin layer (a) to the curable resin layer (B) is in the above-described range.

< resin base Material (C) >

The resin base material (C) is a layer that plays a role of imparting punching workability to the present resin laminate. From this viewpoint, the resin substrate (C) is preferably formed of a resin composition containing at least one of a Polycarbonate (PC) resin, a triacetate cellulose (TAC) resin, a polyethylene terephthalate (PET) resin, a polymethyl methacrylate (PMMA) resin, a methyl methacrylate-styrene copolymer (MS) resin, a polysulfone resin, a norbornene resin, and a cycloolefin resin.

In a preferred application of the present resin laminate, the resin base material (C) is preferably made of a transparent resin.

Among them, the resin base material (C) is particularly preferably formed of a polycarbonate resin from the viewpoint of transparency, impact resistance, heat resistance, and the like.

The polycarbonate resin can be 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 bisphenol a synthesized from bisphenol and acetone.

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

Further, polyester carbonates obtained by polymerization of a copolymer of bisphenol A and a dicarboxylic acid derivative such as terephthalic acid dichloride or the like, and products obtained by polymerization of a bisphenol A derivative such as tetramethylbisphenol A or the like can also be exemplified.

The molecular weight of the polycarbonate-based resin is preferably a molecular weight of viscosity as high as that of a sheet produced by ordinary extrusion molding, and specifically, the viscosity average molecular weight is 15000 to 40000, preferably 20000 to 35000, and more preferably 22000 to 30000.

When the molecular weight is less than the above range, the impact strength of the sheet obtained from the composition is lowered, which is not preferable. On the other hand, if the molecular weight is larger than the above range, the flowability may be lowered and the extrusion moldability may be deteriorated.

< Structure of the present resin laminate >

The resin laminate 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 base material (C).

More specifically, there may be mentioned: (B) the formula (I) includes (A), (B)/(A)/(B), (B)/(A)/(C)/(B), (B)/(C)/(A)/(B), (B)/(A)/(C)/(A) and (B)/(A)/(C)/(A)/(B). Among these structures, a structure in which the curable resin layer (B) is laminated on both surfaces or one surface of the acrylic resin (a) is preferable, and structures of (B)/(a)/(C) and (B)/(a)/(C)/(B) are most preferable.

Fig. 1 is a view showing the structure of one embodiment of the resin laminate of the present invention, and fig. 1(a) shows a scratch-resistant resin laminate 15 having a structure in which a curable resin layer 14 is laminated on one surface of a resin laminate formed by laminating an acrylic resin layer 13 on one surface of a resin substrate 12.

According to this structure, the following advantages are provided: by the synergistic effect of the acrylic resin layer 13 and the curable resin layer 14, even when the thickness of the curable resin layer is as thin as 5 to 15 μm, a high surface hardness can be exhibited, and the like.

Fig. 1(b) shows a scratch-resistant resin laminate 11 in which a curable resin layer 14 is laminated on both surfaces of a resin laminate formed by laminating an acrylic resin layer 13 on one surface of a resin base 12.

According to this structure, the following advantages are provided: since the curable resin layer 14 is also laminated on the resin substrate 12, it is possible to suppress occurrence of process damage or the like on the resin substrate 12. 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 normal hard coat layer.

< production method >

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

The apparatus for producing the resin laminate is composed of, for example, a single main extruder for extruding the polycarbonate resin and a sub-extruder for extruding the acrylic resin constituting the acrylic resin layer. In general, the secondary extruder is a smaller extruder than the primary extruder.

The temperature condition of the main extruder is 230-290 ℃, preferably 240-280 ℃, and the temperature condition of the auxiliary extruder is 220-270 ℃, preferably 230-260 ℃. In order to remove impurities in the resin, a polymer filter is preferably provided upstream of the T-die of the extruder.

As a method of laminating 2 kinds of molten resins by coextrusion, a known method such as a feed block method or a multi-manifold method can be used. At this time, the molten resin laminated by the feeding block is introduced into a sheet molding die such as a T-die, molded into a sheet shape, and then flowed into a molding roll (metal elastic roll or polishing roll) having a mirror-finished surface to form a bank.

The sheet-shaped molded article is subjected to mirror finishing and cooling while passing through a molding roll to form a laminate.

In the case of a multi-manifold die, similarly, the molten resin laminated in the die is molded into a sheet shape inside the die, and then surface-finished and cooled by a molding roll to form a laminated body. The temperature of the die head is generally 210-300 ℃, preferably 230-280 ℃, and the temperature of the forming roller is generally 100-190 ℃, preferably 110-180 ℃. The roll may be a vertical roll or a horizontal roll.

< use >

The resin laminate is useful as a front plate material for a surface protection panel, particularly a mobile phone or a liquid crystal writing pad having a touch panel function, which is disposed on the front surface side (visible side) of an image display device and is used.

< description of terms >

The term "film" generally means a thin and flat product having a very small thickness as compared with the length and width and an arbitrarily defined maximum thickness, and is usually supplied in a roll form (japanese industrial standard JIS k6900), and the term "sheet" generally means a product which is thin as defined in JIS, and generally has a small thickness as compared with the length and width and is flat. However, since the boundaries between the sheet and the film are not definite, and there is no need to distinguish the two in terms of language in the present invention, the term "sheet" is also included in the present invention, and the term "film" is also included in the present invention.

In the present specification, the term "main component" includes, unless otherwise specified, a component that is allowed to contain other components within a range that does not interfere with the function of the main component.

In this case, the content ratio of the main component is not particularly limited, but the main component (in the case of 2 or more main components, the total amount thereof) accounts for 50% by mass or more, preferably 70% by mass or more, and particularly preferably 90% by mass or more (including 100%) of the composition.

In the present invention, unless otherwise specified, the term "X to Y" (X, Y are arbitrary numbers) includes the meaning of "X to Y" and includes the meaning of "preferably larger than X" and "preferably smaller than Y".

In the present invention, the meaning of "preferably larger than X" is included in the case of "X or more" (X is an arbitrary number) unless otherwise specified, and the meaning of "preferably smaller than Y" is included in the case of "Y or less" (Y is an arbitrary number) unless otherwise specified.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples, and various applications can be made without departing from the technical spirit of the present invention.

< measurement and evaluation methods >

First, the methods for measuring and evaluating various physical property values of the samples obtained in examples and comparative examples will be described.

(evaluation of surface hardness)

The resin laminates of examples and comparative examples were measured for pencil hardness on the surface based on the JISK5600-5-4 standard.

(evaluation of scratch resistance)

In the resin laminates of examples and comparative examples, the surface (curable resin layer side) of the resin laminate was subjected to 50 reciprocal wiping with a load of 1000g using #0000 steel wool, and the presence or absence of scratches was visually observed. In table 1, "o" indicates "no damage", "Δ" indicates "damage but practical level", and "x" indicates "damage".

< punching workability >

The resin laminates of examples and comparative examples were subjected to a punching test using a screw press manufactured by Toyo Seiki K.K., using a dumbbell knife according to JIS K6251 in a 20cm square test sample. The evaluation was judged by the presence or absence of cracks in the punched sample piece and the substrate or the presence or absence of cracks in the substrate, and a value of "no cracks or cracks" indicates "cracks or cracks occurred".

< curl test >

As the resin base material, a cured resin layer was formed using a PET film (made of mitsubishi resin, trade name "diafil") 125 μm having a size of a4 by the same method as described in each of examples and comparative examples. The center of each sample was cut into a 10cm square to prepare a test sample. The 4-angle warpage was measured with a ruler and evaluated, and the average of 4 points was used as the curl value of the test specimen.

< example 1>

A laminate a was formed by coextrusion using an extrusion molding machine, a layer formed of a mixture of 80 parts by mass of a polycarbonate resin (product of Mitsubishi engineering plastics corporation, trade name "Lupilon Sl 000") and 20 parts by mass of PCTG (product of SKchemical corporation, trade name "SKYGREEN J2003") as a matrix resin, and a layer formed of an acrylic resin having a dispersed phase of a hard nature (product of Arkema corporation, trade name "AltuglasHT 121") so that the thickness of the matrix resin layer was 560 μm, the thickness of the acrylic resin layer was 140 μm, and the thickness of the laminate was 700 μm. The extrusion conditions were 240 ℃ for the acrylic resin layer, 265 ℃ for the matrix resin layer, R1=110 ℃ for the roll temperature, R2=120 ℃ for R3=125 ℃.

An inorganic hybrid ultraviolet-curable hard coating agent (trade name "EKS 1105", manufactured by DIC) having an inorganic component (silica) content having an ultraviolet-reactive functional group of 15 to 25% by mass), 10 parts by mass of a mixed solution of Irgacure184 (manufactured by Ciba Japan) 0.2 parts by mass and MEK2 parts by mass was applied to the surface of the acrylic resin layer of the laminate a by a bar coater, dried at 70 ℃ for 3 minutes, and then dried at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 1 having a thickness of 5 μm.

< example 2>

An inorganic/inorganic hybrid ultraviolet-curable hard coating agent (manufactured by Momentive, trade name: UVHC 7800) having an ultraviolet-reactive functional group, inorganic component (silica) content: 40 to 50% by mass) was applied to the surface of the acrylic resin layer of the laminate a using a bar coater, dried at 90 ℃ for 1 minute, and then dried at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 2 having a thickness of 6 μm.

< example 3>

A resin laminate 3 having a cured resin layer after drying and a thickness of 6 μm was obtained in the same manner as in example 2, except that polyester-modified polydimethylsiloxane having an acryl group (product name "BYK-UV 3570" manufactured by BYK-chemiee JAPAN) was added as a leveling agent in an amount of 5 parts to 100 parts of the hard coating agent.

< example 4>

An inorganic/inorganic hybrid ultraviolet-curable hard coating agent (5 to 15 mass% of an inorganic component (silica) having an ultraviolet-reactive functional group, trade name "EXCE RATERUA-069 VE", manufactured by Sehinou industries, Ltd.) was applied to the surface of the acrylic resin layer of the laminate a using a bar coater, dried at 90 ℃ for 1 minute, and then applied at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 4 having a thickness of 6 μm.

< example 5>

An inorganic/inorganic hybrid ultraviolet-curable hard coating agent (manufactured by Momentive, trade name: UVHC 7300; content of an 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 a using a bar coater, dried at 90 ℃ for 1 minute, and then dried at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 5 having a thickness of 6 μm.

< example 6>

An acrylic resin having a hard dispersed phase (product of Arkema corporation, trade name "altuglas ht 121") was molded into a laminate b of an acrylic resin layer having a thickness of 700 μm by an extrusion molding machine. The extrusion conditions were extrusion temperature 240 ℃, roll temperature R1 ═ 110 ℃, R2 ═ 120 ℃, R3 ═ 125 ℃.

An organic-inorganic hybrid ultraviolet-curable hard coating agent (manufactured by Momentive, trade name: UVHC 7800) having an ultraviolet-reactive functional group and an inorganic component (silica) content of 40 to 50% by mass) was applied to one surface of the laminate b using a bar coater, dried at 90 ℃ for 1 minute, and then dried at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 6 having a thickness of 6 μm.

< comparative example 1>

A mixed solution of 10 parts by mass of an ultraviolet-curable hard coating agent (trade name "EXCERATERIA-066 VE", manufactured by Seguiya Kogyo Co., Ltd.) containing urethane acrylate as a main component, 0.02 part by mass of Irgacure184 (manufactured by Ciba Japan) and 15 parts by mass of MEK was applied to the surface of the acrylic resin layer of the laminate a by a bar coater, dried at 70 ℃ for 5 minutes, and then dried at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 7 having a thickness of 7 μm.

< comparative example 2>

An ultraviolet-curable hard coating agent (product name: UVHC1101, manufactured by Momentive Co., Ltd.) containing urethane acrylate as a main component was applied to the surface of the acrylic resin layer of the laminate a by a bar coater, dried at 90 ℃ for 1 minute, and then applied at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 8 having a thickness of 8 μm.

< comparative example 3>

A polycarbonate resin (product of Mitsubishi engineering plastics, trade name "Lupilon Sl 000") was molded into a resin sheet c having a thickness of 700 μm by an extrusion molding machine. The extrusion conditions were extrusion temperature 265 ℃, roll temperature R1=110 ℃, R2=120 ℃, R3=125 ℃.

An organic-inorganic hybrid ultraviolet-curable hard coating agent (manufactured by Momentive, trade name: UVHC 7800) having an ultraviolet-reactive functional group and an inorganic component (silica) content of 40 to 50% by mass) was applied to one surface of a resin sheet c using a bar coater, dried at 90 ℃ for 1 minute, and then dried at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 9 having a thickness of 6 μm.

< comparative example 4>

A single-layer resin sheet d having a thickness of 700 μm was molded by an extrusion molding machine using an acrylic resin (product name: ACRYPET VH001, manufactured by Mitsubishi corporation) having no hard dispersed phase. The extrusion conditions were extrusion temperature 240 ℃, roll temperature R1= 100 ℃, R2=110 ℃, R3=125 ℃.

An ultraviolet-curable hard coat agent (trade name "EXCERATERIA-066 VE", manufactured by Seguiya industries, Ltd.) containing urethane acrylate as a main component was applied to one surface of a resin sheet d by a bar coating method, dried at 70 ℃ for 5 minutes, and applied at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 10 having a thickness 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 comprehensive evaluation, the pencil hardness was 7H or more and the value of the curl test was 2mm or less, and those which did not satisfy the above were indicated as "x".

[ Table 1]

From the results shown in table 1, in the case of the urethane acrylate based ultraviolet curable hard coating agents of comparative examples 1 and 2, the pencil hardness of the obtained laminate was 7H, but the curl amount was large and did not reach a practical level.

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

In particular, in the case of the organic-inorganic hybrid ultraviolet-curable hard coating agents of examples 1 to 3 and 6, the pencil hardness of 8H was 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 matrix resin was low, and therefore, a sufficient pencil hardness was not obtained.

From these results, a curable resin layer containing an organic-inorganic hybrid hard coating agent was laminated on the laminate with an acrylic resin, whereby a scratch-resistant resin laminate having higher hardness could be obtained.

In order to further clarify the difference in the curl test in the present example and the comparative example, it is assumed that the PET film was used, and the laminates 1 to 3 also exhibited the same tendency.

< curl test 2>

The cured resin layer was formed by the same method as described in each example and comparative example using the laminate d described below as a resin base material. The central portion of each sample was cut out in a 10cm square to prepare a test sample. The 4-angle warpage was measured with a gauge and evaluated, and the average of 4 points thereof was taken as the curl value in the test sample. The curl value is a value including the thermal expansion amount of the web.

< haze >

NDH5000 (manufactured by Nippon Denshoku industries Co., Ltd.) was used as a test device for a test sample of 5cm square of the resin laminate of each of the examples and comparative examples. The test was carried out in accordance with jis k7136 standard, and the average value thereof was set as the haze value of the test sample.

< example 7>

A laminate d was formed by co-extrusion of a layer formed of a mixture of 80 parts by mass of a polycarbonate resin (product name "CALIBRA 301-4" manufactured by Sumika Styron) as a matrix resin and 20 parts by mass of PCTG (product name "SKYGREENJ 2003" manufactured by SKchemical) and a layer formed of an acrylic resin having a dispersed phase of a rigid property (product name "AltuglasHT 121" manufactured by Arkema) using an extrusion molding machine so that the thickness of the matrix resin layer was 240 μm, the thickness of the acrylic resin layer was 60 μm and the thickness of the laminate was 300 μm. The extrusion conditions were 240 ℃ for the acrylic resin layer, 265 ℃ for the base resin layer, 110 ℃ for the roll temperature R1, 115 ℃ for R2, and 95 ℃ for R3.

An inorganic hybrid ultraviolet-curable hard coating agent (trade name "EKS 1105", manufactured by DIC) having an inorganic component (silica) content having an ultraviolet-reactive functional group of 15 to 25% by mass), 10 parts by mass of a mixed solution of Irgacure184 (manufactured by Ciba Japan) 0.2 parts by mass and MEK2 parts by mass was applied to the surface of the acrylic resin layer of the laminate d by a bar coater, dried at 70 ℃ for 3 minutes, and then dried at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 11 having a thickness of the cured resin layer of 12 μm.

< example 8>

An inorganic/inorganic hybrid ultraviolet-curable hard coating agent (product name: UVHC 7800; manufactured by Momentive Co., Ltd., content of an inorganic component (silica) having an ultraviolet-reactive functional group: 40 to 50% by mass) was applied to the surface of the acrylic resin layer of the laminate d using a bar coater, dried at 90 ℃ for 1 minute, and then dried at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 12 having a thickness of the cured resin layer of 12 μm.

< example 9>

A resin laminate 13 having a thickness of a cured resin layer after drying of 12 μm was obtained in the same manner as in example 2, except that 5 parts of a polyester-modified polydimethylsiloxane having an acryl group (product name "BYK-UV 3570" manufactured by BYK-chemiee JAPAN) was added as a leveling agent to 100 parts of the hard coating agent.

< example 10>

An inorganic/inorganic hybrid ultraviolet-curable hard coating agent (trade name "EXCE RATERUA-069 VE", manufactured by Sehinou industries, Ltd., content of an inorganic component (silica) having an ultraviolet-reactive functional group: 5 to 15% by mass) was applied to the surface of the acrylic resin layer of the laminate d using a bar coater, dried at 90 ℃ for 1 minute, and then applied at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 14 having a thickness of 12 μm.

< example 11>

An inorganic hybrid ultraviolet-curable hard coating agent (product name "UVHC 7300" manufactured by Momentive, Ltd., content of an inorganic component (silica) having an ultraviolet-reactive functional group: 10 to 20% by mass) was applied on the surface of the acrylic resin layer of the laminate d by a bar coating method, dried at 90 ℃ for 1 minute, and then dried at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 15 having a thickness of 12 μm.

< comparative example 5>

A mixed solution of 10 parts by mass of an ultraviolet-curable hard coating agent (trade name "EXCERATERIA-066 VE", manufactured by Seguiya Kogyo Co., Ltd.), 0.02 part by mass of Irgacure184 (manufactured by Ciba Japan) and 15 parts by mass of MEK was applied to the surface of the acrylic resin layer of the laminate d by a bar coater, dried at 70 ℃ for 5 minutes, and then dried at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 16 having a thickness of 12 μm.

< comparative example 6>

An ultraviolet-curable hard coating agent (product name: UVHC1101, manufactured by Momentive Co., Ltd.) containing urethane acrylate as a main component was applied to the surface of the acrylic resin layer of the laminate d using a bar coater, dried at 90 ℃ for 1 minute, and applied at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 17 having a thickness of 12 μm.

The evaluation results of the resin laminates 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 2mm or less, and those which did not satisfy the above were indicated as "x".

[ Table 2]

From the results shown in table 2, it was confirmed that the urethane acrylate based ultraviolet curable hard coating agents of comparative examples 5 and 6 did not reach practical levels in terms of scratch resistance and curling.

On the other hand, in examples 7 to 11, there was almost no curl, and a laminate having a high hardness of 8H or more in pencil hardness was obtained in spite of a thin film base material having a thickness of 300. mu.m. In particular, the highest level of surface hardness of 9H in pencil hardness was achieved in examples 7 to 9, wherein the addition of the leveling agent in example 9 gave an excellent haze value.

The following moldability tests were carried out to confirm the moldability of the present resin laminate.

< moldability >

Vacuum forming was performed using large test samples of the resin laminate a4 of example 12 and comparative example 7. The test conditions were that the molding temperature was 110 ℃, the vacuum pressure was 0.1MPa, the molding time was 10 seconds, the R at the die corner was 2mm, and the depth of deep drawing was 20 mm. The evaluation was carried out by visually evaluating the molded sample, and a circle indicates "no crack" and an x indicates "crack".

< example 12>

A laminate e was formed by coextrusion using an extrusion molding machine, a layer formed of a mixture of 80 parts by mass of a polycarbonate resin (product name "CALIBRA 301-4" manufactured by Sumika Styron) as a matrix resin and 20 parts by mass of PCTG (product name "SKYGREENJ 2003" manufactured by SKchemical) and a layer formed of an acrylic resin having a dispersed phase of a rigid property (product name "AltuglasHT 121" manufactured by Arkema) so that the thickness of the matrix resin layer was 105 μm, the thickness of the acrylic resin layer was 20 μm and the thickness of the laminate was 125 μm. The extrusion conditions were 240 ℃ for the acrylic resin layer, 265 ℃ for the matrix resin layer, 110 ℃ for the roll temperature R1, 110 ℃ for R2, and 80 ℃ for R3.

An inorganic hybrid ultraviolet-curable hard coating agent (product name: UVHC7800F, manufactured by MOMENTVE Co., Ltd.; content of an inorganic component (silica) having an ultraviolet-reactive functional group: 30 to 40% by mass) was applied to the surface of the acrylic resin layer of the laminate e by a bar coating method, dried at 90 ℃ for 1 minute, and then applied at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 18 having a thickness of 10 μm.

< comparative example 7>

A mixed solution of 10 parts by mass of an ultraviolet-curable hard coating agent (trade name "EXCERATERIA-066 VE", manufactured by Seguiya industries, Ltd.) containing urethane acrylate as a main component, 0.02 part by mass of Irgacure184 (manufactured by Ciba Japan) and MEK15 part by mass was applied to the surface of the acrylic resin layer of the laminate e by a bar coating method, dried at 70 ℃ for 5 minutes, and then applied at 500mJ/cm²The cured resin layer was exposed to the above exposure amount to obtain a resin laminate 19 having a thickness 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.

[ Table 3]

The results in Table 3 suggest that the constitution of the present resin laminate can be applied to the application of thermoformability. It is estimated that a moldable resin laminate having low curl and high hardness can be formed by adjusting the thickness ratio of the acrylic resin layer and the curable resin layer.

Claims (19)

1. A scratch-resistant resin laminate having a structure in which a curable resin layer (B) is laminated on both surfaces or one surface of an acrylic resin layer (A), wherein the acrylic resin layer (A) contains an acrylic resin as a main component, and the curable resin layer (B) contains an organic-inorganic hybrid hard coating agent,

the acrylic resin layer (A) is a hard resin layer (a) having a pencil hardness of 3H or more, which is formed by containing or dispersing a hard dispersion phase material in an acrylic resin layer matrix, wherein the hard dispersion phase material is obtained by combining 2 or more thermosetting resins alone or in combination, or is obtained by combining a thermosetting resin and a thermoplastic resin having an unsaturated bond capable of crosslinking with the thermosetting resin,

the organic-inorganic hybrid hard coating agent is composed of a curable resin composition containing an inorganic component having a reactive functional group that is copolymerized with a radical polymerizable monomer and crosslinked, and the thickness of the curable resin layer (B) is in the range of 5 to 15 [ mu ] m,

the surface hardness of the surface on which the curable resin layer (B) is laminated is 7H or more in terms of pencil hardness,

the content of the inorganic component having a reactive functional group in the organic-inorganic hybrid hard coating agent is 5 mass% or more and less than 65 mass%.

2. A scratch-resistant resin laminate having a structure in which a curable resin layer (B) is laminated on at least one side of a resin laminate, wherein the resin laminate is formed by laminating an acrylic resin layer (A) containing an acrylic resin as a main component on both sides or one side of a resin base material (C), and the curable resin layer (B) contains an organic-inorganic hybrid hard coating agent,

the acrylic resin layer (A) is a hard resin layer (a) having a pencil hardness of 3H or more, which is formed by containing or dispersing a hard dispersion phase material in an acrylic resin layer matrix, wherein the hard dispersion phase material is obtained by combining 2 or more thermosetting resins alone or in combination, or is obtained by combining a thermosetting resin and a thermoplastic resin having an unsaturated bond capable of crosslinking with the thermosetting resin,

the organic-inorganic hybrid hard coating agent is composed of a curable resin composition containing an inorganic component having a reactive functional group that is copolymerized with a radical polymerizable monomer and crosslinked, and the thickness of the curable resin layer (B) is in the range of 5 to 15 [ mu ] m,

the surface hardness of the surface on which the curable resin layer (B) is laminated is 7H or more in terms of pencil hardness,

the content of the inorganic component having a reactive functional group in the organic-inorganic hybrid hard coating agent is 5 mass% or more and less than 65 mass%.

3. The scratch-resistant resin laminate according to claim 2, wherein the resin base material (C) contains at least one selected from the group consisting of a Polycarbonate (PC) resin, a cellulose Triacetate (TAC) resin, a polyethylene terephthalate (PET) resin, a polymethyl methacrylate (PMMA) resin, a methyl methacrylate-styrene copolymer (MS) resin, a polysulfone resin, a norbornene-based resin, and a cycloolefin resin.

4. The scratch-resistant resin laminate according to claim 1, wherein the inorganic component having a reactive functional group is ultraviolet-reactive silica.

5. The scratch-resistant resin laminate according to claim 2, wherein the inorganic component having a reactive functional group is ultraviolet-reactive silica.

6. The scratch-resistant resin laminate according to claim 3, wherein the inorganic component having a reactive functional group is ultraviolet-reactive silica.

7. The scratch-resistant resin laminate according to claim 1, wherein the inorganic component in the organic-inorganic hybrid hard coating agent is 10% by mass or more and less than 50% by mass.

8. The scratch-resistant resin laminate according to claim 2, wherein the inorganic component in the organic-inorganic hybrid hard coating agent is 10% by mass or more and less than 50% by mass.

9. The scratch-resistant resin laminate according to claim 3, wherein the inorganic component in the organic-inorganic hybrid hard coating agent is 10% by mass or more and less than 50% by mass.

10. The scratch-resistant resin laminate according to claim 4, wherein the inorganic component in the organic-inorganic hybrid hard coating agent is 10% by mass or more and less than 50% by mass.

11. The scratch-resistant resin laminate according to claim 5, wherein the inorganic component in the organic-inorganic hybrid hard coating agent is 10% by mass or more and less than 50% by mass.

12. The scratch-resistant resin laminate according to claim 6, wherein the inorganic component in the organic-inorganic hybrid hard coating agent is 10% by mass or more and less than 50% by mass.

13. The scratch-resistant resin laminate according to any one of claims 1 to 12, wherein the curable resin layer (B) contains a leveling agent having a reactive functional group at an end thereof.

14. The scratch-resistant resin laminate according to claim 13, wherein the leveling agent is polyether-modified polydimethylsiloxane having an acryloyl group or polyester-modified polydimethylsiloxane having an acryloyl group.

15. The scratch-resistant resin laminate according to any one of claims 1 to 12, wherein the curable resin layer (B) contains a lubricant.

16. The scratch-resistant resin laminate according to claim 13, wherein the curable resin layer (B) contains a lubricant.

17. The scratch-resistant resin laminate according to claim 14, wherein the curable resin layer (B) contains a lubricant.

18. A front plate material for a display device, comprising the scratch-resistant resin laminate according to any one of claims 1 to 17.

19. An image display device having the front plate material of the display device of claim 18.