JP6133808B2 - Method for producing article comprising hard coat laminate - Google Patents

Description

The present invention relates to a method for producing an article comprising a hard coat laminate. More specifically, a method for producing an article comprising a hard coat laminate excellent in transparency, surface hardness, scratch resistance, surface smoothness, and appearance, and can be suitably used as a display face plate of a touch panel or a transparent conductive substrate. About.

2. Description of the Related Art In recent years, touch panels that are installed on image display devices such as liquid crystal displays, plasma displays, and electroluminescent displays and that can be input by touching with a finger or a pen while viewing the display have become widespread.

Conventionally, display panels for touch panels and transparent conductive substrates meet the required properties such as heat resistance, dimensional stability, high transparency, high surface hardness, and high rigidity. Have been used. On the other hand, glass has problems such as low impact resistance and easy cracking, low workability, difficult handling, high specific gravity and heavy, and difficulty in meeting the demands for curved display and flexibility. Therefore, materials that replace glass have been actively studied, and the surface of a transparent resin film substrate such as triacetyl cellulose, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and norbornene-based polymer has excellent surface hardness and scratch resistance. Many hard coat laminated bodies in which a hard coat is formed have been proposed (for example, Patent Document 1). These hard coat laminates are formed into a touch panel display face plate or transparent conductive substrate by cutting, but in order to prevent the hard coat laminate from becoming dirty at that time, a surface protective film It is often performed that a support having an adhesive layer on at least one side is temporarily attached to the hard coat laminate. However, hard coat laminates with improved surface hardness and scratch resistance for touch panel display faceplates and transparent conductive substrates cause defects such as cracks when the support is removed after cutting. There was a problem that it was easy.

JP 2013-208896 A

An object of the present invention is an article comprising a hard coat laminate, which is excellent in transparency, surface hardness, scratch resistance, surface smoothness, and appearance, and can be suitably used as a display face plate of a touch panel or a transparent conductive substrate. It is to provide a manufacturing method.

As a result of diligent research, the present inventor uses heat, active energy rays or the like to lower the adhesive strength between the support and the article to a certain value or less after cutting and before peeling the support from the article. Thus, it has been found that the above-mentioned problems can be achieved.

That is, the present invention is a method for producing an article comprising a hard coat laminate having a hard coat layer and a transparent resin film layer in order from the outermost layer side,
(A) a step of temporarily attaching a support having an adhesive layer on at least one surface and the hard coat laminate;
(B) A step of cutting out the article made of the hard coat laminate using at least one processing method selected from the group consisting of router processing, water jet processing, laser processing, and punching processing;
(C) using at least one selected from the group consisting of heat and active energy rays, and reducing the adhesive strength between the support and the article to 2 N / 2.5 cm or less;
It is a method including.

A second invention is the method according to the first invention, wherein router processing is used in the step (B).

A third aspect of the invention is the method according to the second aspect of the invention, wherein a milling process is performed using a mill whose tip shape is a cylindrical round shape or a tip sphere shape.

A fourth invention is the method according to the second or third invention, wherein the mill is a nicked mill.

A fifth invention is the method according to any one of the second to fourth inventions, wherein the material of the cutting edge of the mill is a cemented carbide.

A sixth invention is the method according to any one of the first to fifth inventions, wherein the hard coat laminate satisfies the following property (A).
(A) The pencil hardness of at least one surface is 7H or more.

A seventh invention is the method according to any one of the first to sixth inventions, wherein the hard coat laminate satisfies the following characteristics (b) and (c).
(B) Total light transmittance of 90% or more.
(C) Haze 2.0% or less.

An eighth invention is the method according to any one of the first to seventh inventions, wherein the hard coat laminate satisfies the following characteristics (d).
(D) The minimum bending radius is 40 mm or less.

A ninth aspect of the invention is the article according to any one of the first to eighth aspects, wherein the article has a curved cutting line having a curvature radius of 0.1 to 20 mm in the plan view. It is a method.

In a tenth aspect of the invention, the hard coat laminate has a hard coat layer (H) and a poly (meth) acrylimide resin layer (α) in order from the outermost layer side. The method according to any one of the inventions.

In an eleventh aspect of the invention, the hard coat laminate includes, in order from the outermost layer side, a first hard coat layer (H1); a poly (meth) acrylimide resin layer (α); a second hard coat layer (H2); The method according to any one of the first to tenth aspects of the present invention.

In a twelfth aspect of the invention, the hard coat laminate includes, in order from the outermost layer side, a first hard coat layer (H1); a first poly (meth) acrylimide resin layer (α1); an aromatic polycarbonate resin layer ( β); second poly (meth) acrylimide resin layer (α2); second hard coat layer (H2); and the α1 layer, β layer, and α2 layer are directly laminated in this order. The method according to any one of the first to eleventh inventions.

A thirteenth invention is an article obtained by the method according to any one of the first to twelfth inventions.

A fourteenth invention is the use of the article according to the thirteenth invention as a touch panel member.

By the manufacturing method of the present invention, without causing a defective phenomenon such as a crack in the hard coat laminate, it is excellent in transparency, surface hardness, scratch resistance, surface smoothness, and appearance, and the touch panel display face plate and transparent conductive material. An article made of a hard coat laminate that can be suitably used as a conductive substrate can be obtained.

The production method of the present invention is a method for producing an article comprising a hard coat laminate having a hard coat layer and a transparent resin film layer in order from the outermost layer side, and (A) a support having an adhesive layer on at least one side Temporarily attaching the body and the hard coat laminate.

The hard coat layer of the hard coat laminate is not limited to one layer, and may be two or more layers. The transparent resin film layer is not limited to one layer, and may be two or more layers. Furthermore, the hard coat laminate may have an arbitrary layer other than the hard coat layer and the transparent resin film layer, if desired. Examples of the optional layer include an anchor coat layer, an adhesive layer, a transparent conductive layer, a high refractive index layer, a low refractive index layer, and an antireflection functional layer.

As described above, the hard coat laminate has at least one hard coat layer, but the article produced by the production method of the present invention can exhibit high surface hardness and scratch resistance. In addition, at least one of the hard coat layers forms the outermost layer of the hard coat laminate.

The hard coat laminate was measured according to the following (1) on the surface of the hard coat layer on the outermost layer side in order to obtain an article that can be suitably used as a display face plate of a touch panel or a transparent conductive substrate. Is preferably 7H or more, more preferably 8H or more, and further preferably 9H or more.

Since the article produced by the production method of the present invention is used as a display face plate of a touch panel or a transparent conductive substrate, the hard coat laminate is required to have high transparency and no coloring. It is done. Therefore, (b) the total light transmittance measured according to the following (2) of the hard coat laminate is usually 85% or more, preferably 90% or more, more preferably 92% or more. A higher total light transmittance is preferable. The (ha) haze measured according to the following (3) is usually 2.5% or less, preferably 2.0% or less, more preferably 1.5% or less. The lower the haze, the better. Furthermore, the yellowness index measured according to the following (7) is preferably 3 or less, more preferably 2 or less, and still more preferably 1 or less.

Furthermore, it is preferable that the said hard-coat laminated body is 40 mm or less in the (d) minimum bending radius measured according to following (4). By satisfying the characteristic (d), the hard coat laminate can be easily handled as a film roll, which is advantageous in terms of production efficiency. The minimum bending radius is preferably as small as possible, more preferably 30 mm or less, and still more preferably 20 mm or less.

The minimum bending radius is a bending radius immediately before a crack is generated on the surface of the bent portion when the hard coat laminate is bent, and is an index indicating the limit of bending. The bending radius is defined in the same way as the curvature radius described later.

The paint for forming the hard coat layer is excellent in transparency, non-colorability, surface hardness, and scratch resistance, except that it can form a hard coat layer having cutting suitability. Any paint can be used without limitation. As a preferable coating material for forming a hard coat layer, an active energy ray-curable resin composition can be exemplified.

The active energy ray-curable resin composition can be polymerized and cured by active energy rays such as ultraviolet rays and electron beams to form a hard coat. Examples of the composition include a compound having two or more isocyanate groups (—N═C═O) and / or a photopolymerization initiator.

Examples of the active energy ray-curable resin include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether. (Meth) acryloyl group-containing prepolymer or oligomer such as (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate Phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl ( (Meth) acrylate and (meth) acryloyl group-containing monofunctional reactive monomers such as trimethylsiloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and styrene; diethylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acrylo (Methoxy) acryloyl group-containing bifunctional reactive monomers such as 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) (Meth) acryloyl group-containing trifunctional reactive monomers such as acrylate and trimethylolethane tri (meth) acrylate; (meth) acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra (meth) acrylate; and dipentaerythritol Examples of the resin include one or more selected from (meth) acryloyl group-containing hexafunctional reactive monomers such as hexaacrylate or the like, or one or more of the above as constituent monomers.

In the present specification, (meth) acrylate means acrylate or methacrylate.

Examples of the compound having two or more isocyanate groups in one molecule include methylene bis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylol of isophorone diisocyanate. Polyisocyanates such as propane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and urethanes such as block isocyanates of the above polyisocyanates A crosslinking agent can be used. These can be used alone or in combination of two or more. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as necessary.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Acetophenone compounds; anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; alkylphenones such as acetophenone dimethyl ketal Compounds; triazine compounds; biimidazole compounds; acyl phosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compounds; hydroxy ketone compounds; and aminobenzoate compounds. it can. These can be used alone or in combination of two or more.

In addition, the active energy ray-curable resin composition includes an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain-preventing agent, a printability improving agent, an antioxidant, and a weathering stabilizer, as desired. In addition, one or more additives such as a light-resistant stabilizer, an ultraviolet absorber, a heat stabilizer, a colorant, and a filler may be included.

Among the optional components used as desired in the active energy ray-curable resin composition, fine particles having a particle diameter of 1 to 300 nm can be mentioned as preferable examples. The surface hardness of the hard coat layer can be increased by using the fine particles in an amount of 1 to 300 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the active energy ray-curable resin component.

As the fine particles, either inorganic fine particles or organic fine particles can be used. Examples of the inorganic fine particles include silica (silicon dioxide); metal oxide fine particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; Examples thereof include metal fluoride fine particles such as magnesium fluoride and sodium fluoride; metal sulfide fine particles; metal nitride fine particles; metal fine particles; Examples of the organic fine particles include resin beads such as a styrene resin, an acrylic resin, a polycarbonate resin, an ethylene resin, and a cured resin of an amino compound and formaldehyde. These can be used alone or in combination of two or more.

In addition, for the purpose of increasing the dispersibility of the fine particles in the paint or increasing the surface hardness of the obtained hard coat layer, the surface of the fine particles is treated with a silane coupling agent such as vinylsilane or aminosilane; a titanate coupling agent; Aluminate coupling agent; organic compound having a reactive functional group such as an ethylenically unsaturated bond group such as (meth) acryloyl group, vinyl group or allyl group or epoxy group; surface treatment agent such as fatty acid or fatty acid metal salt What was processed by etc. may be used.

Among these, in order to obtain a hard coat layer having higher surface hardness, fine particles of silica and aluminum oxide are preferable, and fine particles of silica are more preferable. Examples of commercially available silica fine particles include Snowtex (trade name) manufactured by Nissan Chemical Industries, Ltd., Quartron (trade name) manufactured by Fuso Chemical Industries, Ltd., and the like.

The particle diameter of the fine particles needs to be 300 nm or less in order to maintain the transparency of the hard coat layer. When the particle size is coarse, the effect of improving the surface hardness of the hard coat layer may not be obtained. Preferably it is 200 nm or less, More preferably, it is 120 nm or less. On the other hand, there is no particular lower limit of the particle diameter, but normally available fine particles are fine at most about 1 nm.

In addition, in this specification, the particle diameter of the fine particles is the cumulative value from the smaller particle size in a particle size distribution curve measured using a laser diffraction / scattering particle size analyzer “MT3200II (trade name)” manufactured by Nikkiso Co., Ltd. Is a particle size of 50% by mass.

Moreover, since the said active energy ray curable resin composition is diluted to the density | concentration which is easy to apply, it may contain the solvent as needed. The solvent is not particularly limited as long as it does not react with the components of the curable resin composition and other optional components or does not catalyze (promote) the self-reaction (including degradation reaction) of these components. Examples thereof include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone.

The active energy ray-curable resin composition can be obtained by mixing and stirring these components.

The method for forming the hard coat layer using the hard coat layer forming coating material such as the active energy ray-curable resin composition is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The hard coat layer forming the outermost surface of the hard coat laminate preferably has a thickness of 17 μm or more from the viewpoint of obtaining a pencil hardness of 7H or more. As for the thickness of the said hard-coat layer, 20 micrometers or more are more preferable, and 25 micrometers or more are still more preferable. On the other hand, if the hard coat layer is too thick, the hard coat layer may reduce cutting workability or web handling properties. The thickness of the hard coat layer is preferably 100 μm or less, and more preferably 50 μm or less.

Moreover, it is preferable that the hard coat laminated body has a hard coat layer formed on both outermost surfaces. For example, in the case of a touch panel display faceplate, the required characteristics are usually different between the touch surface and the print surface, but a hard coat layer that matches each required property is applied to the touch surface and the print surface (on both outermost surfaces). It can respond to this by forming. Further, by appropriately adjusting the thickness of each hard coat layer, curling of the hard coat laminate can be suppressed and cutting can be easily performed.

The said transparent resin film layer is a layer used as the transparent film base material for forming the said hard-coat layer. The transparent resin film used for the transparent resin film layer is not limited except that it has high transparency and is not colored, and any transparent resin film can be used. For example, cellulose ester resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate; cyclic hydrocarbon resins such as ethylene norbornene copolymer; acrylic resins such as polymethyl methacrylate and polyethyl methacrylate; (Meth) acrylimide resins; aromatic polycarbonate resins; polyolefin resins such as polypropylene and 4-methyl-pentene-1; polyamide resins; polyarylate resins; polymer urethane acrylate resins; polyimide resins; Examples of the film include non-stretched film, uniaxially stretched film, and biaxially stretched film. The thickness of the transparent resin film is not particularly limited, and can be any thickness as desired. From the viewpoint of handleability when carrying out the method of the present invention, it may be usually 20 μm or more, preferably 50 μm or more. Moreover, from an economical viewpoint, it may be 250 micrometers or less normally, Preferably it may be 150 micrometers or less. When the article obtained by the method of the present invention is used as a display face plate of a touch panel, it may be usually 100 μm or more, preferably 200 μm or more, more preferably 300 μm or more from the viewpoint of maintaining rigidity. Moreover, from a viewpoint of meeting the request | requirement of thickness reduction of a touchscreen, it may be 1500 micrometers or less normally, Preferably it is 1200 micrometers or less, More preferably, it may be 1000 micrometers or less.

The hard coat laminate is excellent in surface hardness, scratch resistance, transparency, surface smoothness, appearance, rigidity, heat resistance, and dimensional stability, and can be suitably used as a display face plate of a touch panel or a transparent conductive substrate. In order to obtain an article that can be produced, it preferably has a hard coat layer (H) and a poly (meth) acrylimide resin layer (α) in order from the outermost layer side.

More preferably, the hard coat laminate has, in order from the outermost layer side, a first hard coat layer (H1); a poly (meth) acrylimide resin layer (α); a second hard coat layer (H2). . Such a hard coat laminate is further excellent in curling resistance, and the workability and work efficiency of the step (B) and the step (C) are increased.

More preferably, the hard coat laminate is, in order from the outermost layer side, the first hard coat layer (H1); the first poly (meth) acrylimide resin layer (α1); the aromatic polycarbonate resin layer (β). A second poly (meth) acrylimide resin layer (α2); a second hard coat layer (H2); and the α1, β, and α2 layers are directly laminated in this order. Such a hard coat laminate has a further improved machinability and further improves the workability and work efficiency of the step (B).

The α layer is a layer made of a poly (meth) acrylimide resin film, and is a layer that becomes a transparent film substrate for forming a hard coat layer. Similarly, the layer in which the α1, β, and α2 layers are directly laminated in this order is a transparent multilayer film, which is a layer that becomes a transparent film substrate for forming the H1 layer and the H2 layer.

Poly (meth) acrylimide resin introduces the characteristics of excellent heat resistance and dimensional stability of polyimide resin while maintaining the high transparency, high surface hardness, and high rigidity characteristics of acrylic resin. It is a thermoplastic resin that has improved the disadvantage of being colored reddish brown, and is disclosed, for example, in JP-T-2011-519999. In the present specification, poly (meth) acrylimide means polyacrylimide or polymethacrylamide.

Preferred poly (meth) acrylimide resins used in the present invention include those having a yellowness index (measured according to JIS K 7105: 1981) of 3 or less. The yellowness index is more preferably 2 or less, and even more preferably 1 or less. In addition, from the viewpoint of extrusion load at the time of forming into a film and the stability of the molten film, the melt mass flow rate (measured in accordance with ISO 1133 at 260 ° C. and 98.07 N) is 0 as a preferable poly (meth) acrylimide resin. 1 to 20 g / 10 min. The melt mass flow rate is more preferably 0.5 to 10 g / 10 min. Further, the glass transition temperature of the poly (meth) acrylimide resin is preferably 150 ° C. or higher from the viewpoint of heat resistance. More preferably, it is 170 degreeC or more.

The poly (meth) acrylimide resin may be a thermoplastic resin other than the poly (meth) acrylimide resin; a pigment, an inorganic filler, an organic filler, and a resin filler, as long as it does not contradict the purpose of the present invention. An additive such as a lubricant, an antioxidant, a weather resistance stabilizer, a heat stabilizer, a mold release agent, an antistatic agent, and a surfactant may be further included. The blending amount of these optional components is usually about 0.01 to 10 parts by mass when the poly (meth) acrylimide resin is 100 parts by mass.

Examples of commercially available poly (meth) acrylimide resins include “PLEXIMID TT70 (trade name)” manufactured by Evonik.

The thickness of the α layer is not particularly limited, and can be any thickness as desired. From the viewpoint of handleability when carrying out the method of the present invention, it may be usually 20 μm or more, preferably 50 μm or more. Moreover, from an economical viewpoint, it may be 250 micrometers or less normally, Preferably it may be 150 micrometers or less. When the article obtained by the method of the present invention is used as a display face plate of a touch panel, it may be usually 100 μm or more, preferably 200 μm or more, more preferably 300 μm or more from the viewpoint of maintaining rigidity. Moreover, from a viewpoint of meeting the request | requirement of thickness reduction of a touchscreen, it may be 1500 micrometers or less normally, Preferably it is 1200 micrometers or less, More preferably, it may be 1000 micrometers or less.

The total thickness of the α1 layer, β layer, and α2 layer is not particularly limited, and can be any thickness as desired. From the viewpoint of handleability when carrying out the method of the present invention, it may be usually 20 μm or more, preferably 50 μm or more. Moreover, from an economical viewpoint, it may be 250 micrometers or less normally, Preferably it may be 150 micrometers or less. When the article obtained by the method of the present invention is used as a display face plate of a touch panel, it may be usually 100 μm or more, preferably 200 μm or more, more preferably 300 μm or more from the viewpoint of maintaining rigidity. Moreover, from a viewpoint of meeting the request | requirement of thickness reduction of a touchscreen, it may be 1500 micrometers or less normally, Preferably it is 1200 micrometers or less, More preferably, it may be 1000 micrometers or less.

The layer thickness of the α1 layer is not particularly limited, but is usually 20 μm or more from the viewpoint of keeping the surface hardness high so that the article obtained by the method of the present invention can be suitably used as a display face plate of a touch panel. It may be 40 μm or more, more preferably 60 μm or more. The layer thickness of the α2 layer is not particularly limited, but is preferably the same as the α1 layer from the viewpoint of curl resistance of the hard coat laminate. The layer thickness of the β layer is not particularly limited, but is usually 20 μm or more, preferably 80 μm or more, and more preferably 120 μm or more from the viewpoint of cutting resistance of the hard coat laminate.

Here, the “same layer thickness” should not be interpreted as the same layer thickness in a physicochemically strict sense. It should be construed that the layer thickness is the same within the range of process and quality control that is usually performed industrially. This is because the curl resistance of the transparent multilayer film can be kept good if the layer thickness is the same within the range of the amplitude of process and quality control that is usually performed industrially. In the case of an unstretched multilayer film manufactured by the T-die coextrusion method, the process and quality are usually controlled with a width of about −5 to +5 μm, and therefore the layer thickness of 65 μm and 75 μm are interpreted as the same. Should be.

As the poly (meth) acrylimide resin used for the α1 layer and the α2 layer, the same resins as those used for the α layer can be used.

The poly (meth) acrylimide-based resin used for the α1 layer and the poly (meth) acrylimide-based resin used for the α2 layer have different resin characteristics, for example, poly (meth) with different melt mass flow rate and glass transition temperature. A (meth) acrylimide resin may be used, but from the viewpoint of curling resistance of the transparent multilayer film, it is preferable to use one having the same resin characteristics. For example, using the same lot of the same grade is one preferred embodiment.

Examples of the aromatic polycarbonate resin used for the β layer include aromatic dihydroxy compounds such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and phosgene. A polymer obtained by an interfacial polymerization method with an aromatic dihydroxy compound such as bisphenol A, dimethyl bisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and carbonic acid such as diphenyl carbonate. One or a mixture of two or more aromatic polycarbonate resins such as a polymer obtained by a transesterification reaction with a diester can be used.

As a preferable optional component that can be included in the aromatic polycarbonate-based resin, a core-shell rubber can be exemplified. When the total of the aromatic polycarbonate-based resin and the core-shell rubber is 100 parts by mass, the core-shell rubber is 0-30 parts by mass (aromatic polycarbonate-based resin 100-70 parts by mass), preferably 0-10 parts by mass (aromatic By using it in an amount of 100 to 90 parts by mass of the polycarbonate-based resin, it is possible to further improve the cutting resistance and impact resistance of the aromatic polycarbonate-based resin layer.

Examples of the core shell rubber include methacrylic ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic. Mention one or a mixture of two or more core-shell rubbers such as acid ester graft copolymers, methacrylate ester / acrylate rubber graft copolymers, methacrylate ester / acrylonitrile / acrylate rubber graft copolymers Can do.

The aromatic polycarbonate-based resin may be a thermoplastic resin other than the aromatic polycarbonate-based resin and the core-shell rubber; a pigment, an inorganic filler, an organic filler, a resin filler; An additive such as an antioxidant, a weather resistance stabilizer, a heat stabilizer, a mold release agent, an antistatic agent, and a surfactant may be further included. The compounding amount of these optional components is usually about 0.01 to 10 parts by mass when the total of the aromatic polycarbonate resin and the core-shell rubber is 100 parts by mass.

The production method for obtaining the poly (meth) acrylimide-based resin film is not particularly limited. For example, (a) a poly (meth) acrylimide is used from a T die using an apparatus including an extruder and a T die. A step of continuously extruding a molten film of a resin; (b) the poly (meth) acrylic between the rotating or circulating first mirror body and the rotating or circulating second mirror body; And a step of supplying and pressing a molten film of an imide-based resin.

Similarly, a production method for obtaining a transparent multilayer film in which the α1 layer, the β layer, and the α2 layer are directly laminated in this order is not particularly limited. For example, (a ′) a co-planar including an extruder and a T die. Using an extrusion device, the first poly (meth) acrylimide resin layer (α1); the aromatic polycarbonate resin layer (β); the second poly (meth) acrylimide resin layer (α2); A step of continuously co-extruding a laminated transparent multilayer film melt film from a T-die; (b ′) a rotating or circulating first mirror body and a rotating or circulating second mirror body; In the meantime, a method including supplying and pressing the molten film of the transparent multilayer film may be mentioned.

As the T die used in the step (a) or the step (a ′), an arbitrary one can be used, and examples thereof include a manifold die, a fish tail die, and a coat hanger die.

Any coextrusion apparatus can be used, and examples thereof include a coextrusion apparatus such as a feed block system, a multi-manifold system, and a stack plate system.

Any extruder can be used as the extruder used in the step (a) or the step (a ′). For example, a single-screw extruder, a co-rotating twin-screw extruder, and a bi-directional rotating machine An example is a screw extruder.

In addition, in order to suppress deterioration of the poly (meth) acrylimide resin or the aromatic polycarbonate resin, it is one of preferable methods to purge the inside of the extruder with nitrogen.

Furthermore, since the poly (meth) acrylimide resin is a highly hygroscopic resin, it is preferably dried before being used for film formation. It is also one of preferable methods that the poly (meth) acrylimide resin dried by a dryer is directly transported from the dryer to the extruder and charged. The set temperature of the dryer is preferably 100 to 150 ° C. It is also a preferred method to provide a vacuum vent in the metering zone of the extruder, usually at the tip of the screw.

The temperature of the T die used in the step (a) or the step (a ′) is a continuous extrusion or coextrusion of a molten film of a poly (meth) acrylimide resin or a molten film of the transparent multilayer film. In order to perform the process to perform stably, it is preferable to set it at least 260 degreeC or more. More preferably, it is 270 degreeC or more. Moreover, in order to suppress deterioration of poly (meth) acrylimide resin or aromatic polycarbonate resin, the temperature of the T die is preferably set to 350 ° C. or lower.

The ratio (R / T) of the lip opening (R) to the thickness (T) of the resulting poly (meth) acrylimide resin film or transparent multilayer film is preferably 1 to 5. More preferably, it is 1.1-2.5. When the ratio (R / T) exceeds 5, the retardation may increase. If it is less than 1, the extrusion load may become excessive.

As said 1st mirror surface body used at the said process (b) or the said process (b '), a mirror roll, a mirror belt, etc. can be mention | raise | lifted, for example. As said 2nd mirror surface body, a mirror surface roll, a mirror surface belt, etc. can be mention | raise | lifted, for example.

The mirror roll is a roll having a mirror-finished surface, and is made of metal, ceramic, silicon rubber, or the like. Further, the surface of the mirror roll can be subjected to chrome plating, iron-phosphorus alloy plating, hard carbon treatment by PVD method or CVD method, etc. for the purpose of protection from corrosion and scratches.

The mirror belt is a seamless belt made of a normal metal whose surface is mirror-finished. For example, the mirror belt is circulated between a pair of belt rollers. Further, the surface of the mirror belt can be subjected to chrome plating, iron-phosphorus alloy plating, hard carbon treatment by PVD method or CVD method for the purpose of protection from corrosion and scratches.

By the film forming method, a poly (meth) acrylimide resin film or a transparent multilayer film excellent in transparency, surface smoothness, and appearance can be obtained. This is because the melted film of the poly (meth) acrylimide resin film or the transparent multilayer film is pressed between the first mirror body and the second mirror body, so that the first mirror body and the second mirror body are highly smooth. It can be considered that the surface state is transferred to the film and a defective portion such as a die stripe is corrected.

The surface temperature of the first mirror body is preferably 100 ° C. or higher so that the transfer of the surface state can be performed satisfactorily. More preferably, it is 120 degreeC or more, More preferably, it is 130 degreeC or more. Moreover, in order to prevent the appearance defect (peeling trace) accompanying peeling with the first mirror body from appearing on the film, the surface temperature of the first mirror body is preferably 200 ° C. or lower, more preferably 160 ° C. or lower.

The surface temperature of the second mirror body is preferably set to 20 ° C. or higher so that the transfer of the surface state can be performed satisfactorily. More preferably, it is 60 degreeC or more, More preferably, it is 100 degreeC or more. Moreover, in order to prevent the appearance defect (peeling trace) accompanying peeling with the second mirror surface from appearing on the film, the surface temperature of the second mirror surface is preferably 200 ° C. or lower, more preferably 160 ° C. or lower.

The surface temperature of the first mirror body is preferably higher than the surface temperature of the second mirror body. This is because the film is held in the first mirror body and sent to the next transfer roll.

Moreover, when forming the hard coat layer, on the hard coat layer forming surface of the poly (meth) acrylimide resin film and the transparent multilayer film to be a transparent film substrate for forming the hard coat layer, or on both surfaces, In order to increase the adhesive strength with the hard coat layer, easy adhesion treatment such as corona discharge treatment or anchor coat layer formation may be performed in advance.

When the corona discharge treatment is performed, good interlayer adhesion strength can be obtained by setting the wetting index (measured in accordance with JIS K6768: 1999) to usually 50 mN / m or more, preferably 60 mN / m or more. become. Further, after the corona discharge treatment, an anchor coat layer may be further formed.

In the corona discharge treatment, a film is passed between an insulated electrode and a dielectric roll, a high frequency high voltage is applied to generate a corona discharge, and the film surface is treated. Oxygen and the like are ionized by the corona discharge and collide with the film surface, so that the resin molecular chain is broken or the oxygen-containing functional group is added to the resin molecular chain on the film surface, and the wetting index is increased.

The unit area and the treatment amount (S) per unit time of the corona discharge treatment are determined from the viewpoint of obtaining the above wetting index, and are usually 80 W · min / m ² or more, preferably 120 W · min / m ² or more. . In addition, if the processing amount (S) is too high, the film is deteriorated. Therefore, the processing amount (S) is preferably suppressed to 500 W · min / m ² or less. More preferably, it is 400 W · min / m ² or less.

The processing amount (S) is defined by the following equation.
S = P / (L ・ V)
Here, S: treatment amount (W · min / m ² ), P: discharge power (W), L: length of discharge electrode (m), V: line speed (m / min).

The anchor coating agent for forming the anchor coating layer is not limited except that it has high transparency and is not colored, such as polyester, acrylic, polyurethane, acrylic urethane, and polyester urethane. The well-known thing can be used. Among these, a thermoplastic urethane anchor coating agent is preferable from the viewpoint of improving the adhesive strength with the hard coat layer.

As the anchor coating agent, a paint containing a silane coupling agent can also be used. Silane coupling agents include hydrolyzable groups (for example, alkoxy groups such as methoxy group and ethoxy group; acyloxy groups such as acetoxy group; halogen groups such as chloro group; and the like) and organic functional groups (for example, amino groups, A silane compound having at least two different reactive groups such as a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, and an isocyanate group, and functions to improve the adhesive strength with the hard coat layer. Of these, a silane coupling agent having an amino group is preferable from the viewpoint of improving the adhesive strength with the hard coat layer.

The paint containing the silane coupling agent is a paint mainly containing a silane coupling agent (50% by mass or more as a solid content). Preferably, 75% by mass or more, more preferably 90% by mass or more of the solid content of the paint is the silane coupling agent.

Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N- 2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, and the like, and one or a mixture of two or more thereof can be used. Can be used.

The method for forming the anchor coat layer is not limited, and a known web coating method can be used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating. At this time, any dilution solvent such as methanol, ethanol, 1-methoxy-2-propanol, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and acetone can be used as necessary. .

Further, the anchor coating agent includes an antioxidant, a weather resistance stabilizer, a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, an antistatic agent, a surfactant, and a colorant as long as the object of the present invention is not adversely affected. In addition, one or two or more additives such as an infrared shielding agent, a leveling agent, a thixotropic agent, and a filler may be included.

The thickness of the anchor coat layer is usually about 0.01 to 5 μm, preferably 0.1 to 2 μm.

The support is also called a protective film, support film, process paper, etc., and has an adhesive layer on at least one side of the film substrate, and the resulting article becomes dirty when the hard coat laminate is cut. In order to prevent this, the hard coat laminate is temporarily attached to at least one side, usually both sides. The support is usually peeled off and removed from the article when the article is incorporated as a member such as a touch panel.

As an adhesive for forming the adhesive layer of the support, the adhesive strength between the support and the article is 2 N / 2.5 cm or less using heat or active energy rays in the following step (C). Any pressure-sensitive adhesive can be used without particular limitation as long as it can be lowered. Further, after the step (C), it is preferable to use a pressure-sensitive adhesive that can be peeled off cleanly without leaving glue when the support is peeled off from the article. The thickness of the pressure-sensitive adhesive layer is arbitrary and is not particularly limited, but is usually 0.5 to 200 μm.

In this specification, the adhesive strength is determined by cutting out a test piece having a width of 25 mm and a length of 80 mm, adjusting the condition for 24 hours or more in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and then testing speed of 300 mm / It is the adhesive strength when a 180 ° peel test is performed under the condition of minutes. When the support was peeled off from the article, it was folded at 180 ° with the end of the support so that the back of the support overlapped, and peeled off 25 mm from the article. One end of the peeled article was fixed to one chuck of the tensile tester, and a support was fixed to the other chuck. Further, after the measurement was started, the first 15 mm length measurement value was ignored, and the subsequent 25 mm length adhesive strength measurement values were averaged and used as the peel strength value for calculating the adhesive strength. The above test method is basically in accordance with JIS Z 0237: 2009. However, the sample size and the like are changed from the JIS standard so that a sample collected from a display face plate for a smartphone can also be measured.

As such an adhesive, as a type that can reduce the adhesive strength by thermosetting or active energy ray curing, for example, two or more reactive functional groups in one molecule, for example, amino group, vinyl group , An adhesive having an epoxy group, a methacryloxy group, an acryloxy group, and an isocyanate group; an adhesive composition comprising the adhesive and at least one or more of an isocyanate curing agent, a photopolymerization initiator, and an organic peroxide And so on. Examples of the type that can be foamed by heat or active energy rays and reduce the adhesive strength by reducing the true adhesive area include an adhesive containing a foaming agent.

The isocyanate-based curing agent is a compound having two or more isocyanate groups in one molecule, and examples thereof include those described above in the description of the hard coat layer. One or a mixture of two or more of them can be used. Can be used.

As said photoinitiator, what was mentioned above in description of a hard-coat layer can be mention | raise | lifted, for example, Those 1 type, or 2 or more types of mixtures can be used.

Examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl- 2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane , N-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxide Oxyisopropyl carbonate, diacetyl peroxide Lauroyl peroxide, tert- and butyl cumyl peroxide can be mentioned, it is possible to use one kind of them or a mixture of two or more thereof.

Examples of the foaming agent include thermal expansion microcapsules; azo compounds such as azodicarboxylic acid amide; nitroso compounds such as N, N′-dinitrosopentamethylenetetramine; hydrogencarbonates such as sodium hydrogencarbonate and ammonium hydrogencarbonate; Examples thereof include organic acids such as citric acid, sodium citrate, and succinic acid; sodium borohydride; water; and the like, and one or a mixture of two or more thereof can be used.

Examples of the film substrate include unstretched films such as polyethylene resins, unstretched films such as polypropylene resins and polyethylene terephthalate resins, uniaxially stretched films, and biaxially stretched films. Although the thickness of a film base material is arbitrary and it does not restrict | limit in particular, Usually, it is 10-1000 micrometers.

As a commercially available example of such a pressure-sensitive adhesive or a support having such a pressure-sensitive adhesive layer, Fujikura Kasei Co., Ltd. “Acrybase LKG-1701 (trade name) ) ”,“ Acrybase LKG-1702 (trade name) ”, etc .;“ Riva Alpha (trade name) ”manufactured by Nitto Denko Corporation can be cited as a type of support that reduces the adhesive strength by thermal foaming. .

The manufacturing method of the present invention cuts out the article made of the hard coat laminate by at least one processing method selected from the group consisting of (B) router processing, water jet processing, laser processing, and punching processing. A process.

Router processing is a processing method in which cutting is performed by a mill that rotates at a high speed, and the finish of the cut surface is smooth. It is also computer controlled and has excellent dimensional stability and reproducibility.

Water jet processing is a method of spraying water pressurized to ultra-high pressure (up to about 4000 atm.) From an extremely small nozzle (usually about 0.1 mmΦ), and energy of high-speed and high-density ultra-high-pressure water. This is a processing method for cutting, and is excellent in that the thermal influence on the workpiece is small. In some cases, an abrasive is mixed with water.

Laser processing is a processing method in which the material of the part of the workpiece is melted and evaporated to be cut by focusing the laser beam on the part of the workpiece to be cut.

The punching process is a processing method in which a workpiece is placed on a Thomson mold having a steel blade placed on a support stand and punched by pressing. The mold is inexpensive, has a high degree of freedom in handling various shapes, and is excellent in productivity.

Among these, router processing and laser processing are preferable, and router processing is more preferable.

Further, as a mill used in the router processing, a mill having a round tip or a spherical tip can be preferably used. As a result, an article having a hard coat layer having a higher surface hardness can be produced without any problem.

Here, the mill whose tip shape is a round cylindrical shape is a substantially conical mill with rounded vertices as shown in the conceptual diagram of FIG. 2, and the blade is spiral from the apex (including the vicinity). It is attached to the shape.

Further, the mill with the tip shape of the tip of the blade is a tip sphere type, as shown in the conceptual diagram of FIG. 3 or FIG. 4, is a mill whose tip is substantially spherical or semi-spherical. It is attached in a spiral shape from the top (including the vicinity) of the hemisphere.

There are 2 blades, 3 blades, 4 blades, and a large number of 5 or more blades (sometimes called rotary blades), and any of them can be used, but preferably Is a four-blade or rotary blade. It is possible to increase the processing speed and clean the finish of the cutting edge.

As the mill, a nicked mill can be preferably used. The cutting waste generated by the router processing is surely discharged without adhering to the article.

Here, the nicked mill has a spiral groove extending from the spiral blade to the blade support rod so that it continues from the groove between the blade as shown in the conceptual diagram of FIG. It is a mill that has been.

Further, as the mill, a mill whose blade edge is made of cemented carbide can be preferably used. As a result, an article having a hard coat layer having a higher surface hardness can be produced without any problem.

The cemented carbide is a composite material obtained by sintering carbides of Group 4a, 5a, and 6a metals with an iron-based metal such as iron, cobalt, or nickel. For example, a tungsten carbide-cobalt alloy, Tungsten carbide-titanium carbide-cobalt alloy, tungsten carbide-tantalum carbide-cobalt alloy, tungsten carbide-titanium carbide-tantalum carbide-cobalt alloy, tungsten carbide-nickel alloy, tungsten carbide-nickel-chromium alloy, etc. Can give.

Also, hard materials such as titanium nitride, titanium carbonitride, titanium aluminum nitride, and aluminum chrome nitride are used for chemical vapor deposition and physical vapor deposition on the surface of the mill whose cutting edge material is cemented carbide. The method may be used for coating.

The production method of the present invention uses (C) at least one selected from the group consisting of heat and active energy rays, and reduces the adhesive strength between the support and the article to 2 N / 2.5 cm or less. ;including.

When the article is used as a touch panel member, the support is peeled off and removed. However, when the adhesive strength between the support and the article is high, a large stress is applied to bend the article when the support is peeled off, and a defective phenomenon such as cracking of the article tends to occur. On the other hand, in the step (B) for cutting out the article, if the adhesive strength between the support and the article is not high to some extent, the support is rolled up and the object of preventing dirt cannot be achieved. Therefore, in the present invention, after the step (B), the adhesive strength between the support and the article is reduced to 2 N / 2.5 cm or less using heat or active energy rays, and the article is peeled off when the support is peeled off. In this case, a stress such as bending is hardly applied, and a defect phenomenon such as a crack in the article is suppressed.

The adhesive strength is preferably 2 N / 2.5 cm or less, more preferably 1.5 N / 2.5 cm or less, and even more preferably 1.0 N / 2.5 cm, in order to suppress defective phenomena such as cracks in the article. It is as follows. On the other hand, until the article is used as a touch panel member, the support is preferably 0.01 N / 2.5 cm or more, more preferably 0.05 N / 2 so that the support can achieve the purpose of preventing contamination. .5 cm or more.

The method for reducing the adhesive strength using heat is not limited except that heat is used, and any method can be used. For example, the article cut out in the above step (B) (with a support at this stage) is passed through a tunnel furnace heated to a desired temperature at a speed that will result in a desired residence time in the furnace. For example, a method of bringing a hot plate or metal roll preheated to a desired temperature into contact with a desired time and pressure; a method of irradiating near infrared light with a desired intensity and time; and the like.

The method of reducing the adhesive strength using an active energy ray is not limited except that an active energy ray is used, and an arbitrary method can be used. For example, the apparatus which uses a high pressure mercury lamp, a metal halide lamp, etc. as a light source, and irradiates the article cut out by the said process (B) of 10-10000 mJ / cm < ² > etc. can be mention | raise | lifted.

Moreover, before the said process (C), the adhesive strength of the said support body and the said article becomes like this. Preferably it is 3-12 N / 2.5cm. Within this range, the purpose of preventing contamination in the step (B) can be reliably achieved, and the adhesive strength can be easily reduced to 2 N / 2.5 cm or less in the step (C).

Since the article obtained by the production method of the present invention is used as a display face plate of a touch panel or a transparent conductive substrate, in order to provide a cutting line when cutting from the hard coat laminate by cutting, an opening or the like in the article Usually, the cutting line has a curved cutting line with a radius of curvature of 0.1 to 20 mm in the plan view of the article. The manufacturing method of the present invention is a method that can be obtained without causing defects such as cracks in the hard coat, even if the article has a curved cutting line with a small curvature radius as described above.

The radius of curvature is defined as follows. The length from the M point to the N point of the curve is ΔS; the difference between the slope of the tangent at the M point and the slope of the contact point at the N point is Δα; a straight line perpendicular to the tangent at the M point and intersecting at the M point When the intersection point with a straight line that is perpendicular to the tangent line at the N point and intersects at the N point is O; and when ΔS is sufficiently small, the curve from the M point to the N point can be approximated to an arc. (FIG. 6). The radius at this time is defined as the radius of curvature. When the radius of curvature is R, ∠MON = Δα, and when ΔS is sufficiently small, Δα is also sufficiently small, so ΔS = RΔα is established, and R = ΔS / Δα.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

Measuring method (1) Pencil hardness (surface hardness)
In accordance with JIS K 5600-5-4, measurement was performed using a pencil “Uni (trade name)” manufactured by Mitsubishi Pencil Co., Ltd. under a load of 750 g. In the table, the measurement value on the touch surface side / measurement value on the printing surface side is described.

(2) Total light transmittance According to JIS K 7361-1: 1997, it measured using the turbidimeter "NDH2000 (brand name)" of Nippon Denshoku Industries Co., Ltd.

(3) According to haze JIS K 7136: 2000, it measured using the turbidimeter "NDH2000 (brand name)" of Nippon Denshoku Industries Co., Ltd.

(4) For a test piece conditioned at a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50 ± 5% for 24 hours with reference to the bending formability (Method B) of the minimum bending radius JIS-K6902, the bending temperature is 23 ° C. ±. 2 ° C., the fold line is in a direction perpendicular to the machine direction of the hard coat laminate, and the hard coat layer on the outermost layer side (the touch surface when it becomes an article) is the outer side. It was made to be bent so that a curved surface was formed. Among the forming jigs in which no cracks occurred, the radius of the front part of the smallest front part radius was defined as the minimum bending radius.

(5) Cutting workability (state of curved cutting line)
About the cutting hole whose both ends are curvature radius 0.5mm, the cutting end surface of the both ends was observed visually or with a microscope (100 times), and evaluated according to the following criteria. Moreover, about the circular cutting hole of radius 0.1mm, the cutting end surface was observed visually or a microscope (100 times), and the following references | standards evaluated. The table shows the former results-the latter results in this order.
A: No cracks or whiskers are observed even under microscopic observation. O: No cracks are observed even under microscopic observation. But beards are allowed.
(Triangle | delta): A crack is not recognized visually. However, cracks are observed by microscopic observation.
X: Cracks are recognized visually.

(6) Surface smoothness (surface appearance)
The surface (both surfaces) of the article was visually observed while being applied with various incident angles of the fluorescent light, and evaluated according to the following criteria.
A: There is no wave or scratch on the surface. There is no cloudiness even when looking at the light up close.
○: There is a part with a slight cloudiness when looking closely at the light.
Δ: Slight swells and scratches are observed on the surface when viewed closely. There is also a cloudiness.
X: Many undulations and scratches can be observed on the surface. There is also a clear cloudiness.

(7) Color tone According to JIS K 7105: 1981, the yellowness index (YI) was measured using a chromaticity meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation.

(8) Linear expansion coefficient It was measured according to JIS K 7197: 1991. A thermomechanical analyzer (TMA) “EXSTAR6000 (trade name)” manufactured by Seiko Instruments Inc. was used. The test piece was 20 mm in length and 10 mm in width, and the transparent film substrate was collected so that the machine direction of the test piece was the vertical direction of the test piece. The distance between chucks was 10 mm, and the temperature program was a program in which the temperature was maintained at 20 ° C. for 3 minutes, and then the temperature was increased to 270 ° C. at a temperature increase rate of 5 ° C./min. The linear expansion coefficient was calculated from the obtained temperature-test piece length curve as a low temperature side temperature of 30 ° C. and a high temperature side temperature of 250 ° C.

(9) The scratch-resistant article was placed on a JIS L 0849 Gakushin Tester so that the touch surface side hard coat surface of the article was the surface. Subsequently, after # 0000 steel wool was attached to the friction terminal of the Gakushin Tester, a load of 500 g was placed, and the surface of the test piece was rubbed 100 times. The surface was visually observed and evaluated according to the following criteria.
◎: No scratch ○: There are 1 to 5 scratches Δ: There are 6 to 10 scratches ×: There are 11 or more scratches

Raw materials used (α) Poly (meth) acrylimide resin:
(Α-1) Poly (meth) acrylimide “PLEXIMID TT70 (trade name)” manufactured by Evonik.

(Β) Aromatic polycarbonate resin:
(Β-1) Aromatic polycarbonate “Caliver 301-4 (trade name)” by Sumika Stylon Polycarbonate Co., Ltd.

(Γ) Hard coat forming paint (γ-1)
The following component γa 50 parts by mass, the following component γb 50 parts by mass, the following component γc 50 parts by mass, the following component γd 2 parts by mass, the following component γe 1 part by mass, the following component γg 4 parts by mass, the following component γh 1 part by mass, and It was obtained by mixing and stirring 20 parts by mass of the following component γi.
(Γ-2)
50 parts by mass of the following component γa, 50 parts by mass of the following component γb, 50 parts by mass of the following component γc, 2 parts by mass of the following component γd, 0.5 parts by mass of the following component γf, 4 parts by mass of the following component γg, 1 part by mass of the following component γh And 20 parts by mass of the following component γi were obtained by mixing and stirring.
(Γ-3)
25 parts by mass of the following component γa, 75 parts by mass of the following component γb, 50 parts by mass of the following component γc, 2.5 parts by mass of the following component γd, 1 part by mass of the following component γe, 4 parts by mass of the following component γg, 1 part by mass of the following component γh And 25 parts by mass of the following component γi were obtained by mixing and stirring.
(Γ-4)
100 parts by mass of the following component γb, 50 parts by mass of the following component γc, 3 parts by mass of the following component γd, 0.5 parts by mass of the following component γf, 4 parts by mass of the following component γg, 1 part by mass of the following component γh, and 30 parts by mass of the following component γi Parts were obtained by mixing and stirring.

(Γa) Dipentaerythritol hexaacrylate of Nippon Kayaku Co., Ltd.
(Γb) 50:50 (mass ratio) mixed paint “Laromer PO9026 (trade name)” of polyether acrylate and nano silica (average particle diameter 20 nm) manufactured by BASF.
(Γc) Surface-modified nanosilica (average particle size 15 nm) from Nissan Chemical Industries, Ltd. Methyl isobutyl ketone dispersion (solid content 30% by mass) “MIBK-ST (trade name)”.
(Γd) Acrylic silane coupling agent (3-acryloxypropyltrimethoxysilane “KBM-5103 (trade name)” manufactured by Shin-Etsu Chemical Co., Ltd.
(Γe) A fluorine-based water repellent “Fluorolink AD1700 (trade name) manufactured by Solvay Solexis.
(Γf) Surface conditioning agent “BYK-399 (trade name)” of Big Chemie Japan, Inc.
(Γg) Phenylketone-based photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) “SB-PI714 (trade name)” of Sojyo Sangyo Co., Ltd.
(Γh) Trifunctional polyisocyanate “Coronate HX (trade name)” by Nippon Polyurethane Industry Co., Ltd.
(Γi) 1-methoxy-2-propanol.

(Δ) Support (δ-1)
Fujikura Kasei Co., Ltd. UV curable adhesive “Acrybase LKG-1702 (trade name)” 100 parts by mass; Fujikura Kasei Co., Ltd. isocyanate curing agent “LKG-17HN02 (trade name)” 6.1 parts by mass; Fujikura A photopolymerization initiator “KN-101 (trade name)” 0.85 parts by mass from Kasei Corporation; and 50 parts by mass of ethyl acetate; Using a film Mayer bar type coating device on one side of the film, coating was carried out so that the thickness of the pressure-sensitive adhesive after drying was 10 μm to obtain a support.

(Δ-2)
Fujikura Kasei Co., Ltd. UV curable adhesive “Acrybase LKG-1701 (trade name)” 100 parts by mass; Fujikura Kasei Co., Ltd. isocyanate curing agent “LKG-17HN01 (trade name)” 3.0 parts by mass; Fujikura A pressure-sensitive adhesive obtained by mixing and stirring 1.5 parts by mass of a photopolymerization initiator “KN-101 (trade name)” of Kasei Corporation; and 50 parts by mass of ethyl acetate; Using a film Mayer bar type coating device on one side of the film, coating was carried out so that the thickness of the pressure-sensitive adhesive after drying was 10 μm to obtain a support.

(A) Transparent resin film substrate (a1) Transparent multilayer film:
Using the coextrusion film forming apparatus having the configuration shown in FIG. 6, the above (α-1) is used as both outer layers (α1 layer and α2 layer) of the molten film of the transparent multilayer film by the extruder 1, and the above (β-1) As the intermediate layer (β layer) of the melt film of the transparent multilayer film by the extruder 2, α1 layer; β layer; α2 layer; Continuously extruded from the multi-manifold coextrusion T-die 3 and between the rotating mirror surface roll 5 and the mirror belt 6 circulating along the outer peripheral surface of the mirror surface roll so that the α1 layer is on the mirror surface roll 5 side. Supplying and pressing was performed to obtain a transparent multilayer film having a total thickness of 250 μm, an α1 layer thickness of 80 μm, a β layer thickness of 90 μm, and an α2 layer thickness of 80 μm. At this time, the setting condition is that the drying temperature before film formation is (α-1) is 150 ° C and (β-1) is 100 ° C; the setting temperature of the extruder 1 is C1 / C2 / C3 / C4 / C5 / AD = 260 / 290-290 ° C; set temperature of extruder 2 is C1 / C2 / C3 / C4 / C5 / C6 / AD = 260/280/280 / 260-260 / 270 ° C; Perform nitrogen purge and use vacuum vent; T die 3 set temperature 300 ° C., lip opening 0.5 mm; mirror roll 5 set temperature 130 ° C .; mirror belt 6 set temperature 120 ° C., pressure 1.4 MPa; The speed was 6.5 m / min.

(A2) Single layer film of poly (meth) acrylimide resin:
Using (α-1) above, a 50 mm extruder (with a W flight screw of L / D = 29, CR = 1.86); a T die having a die width of 680 mm; pressing a molten film with a mirror roll and a mirror belt A film having a thickness of 250 μm was obtained using an apparatus equipped with a winder equipped with a mechanism for At this time, the setting conditions of the extruder are C1 / C2 / C3 / AD = 280/300/320/320 ° C .; T die setting temperature 320 ° C .; T die lip opening 0.5 mm; Set temperature 140 ° C .; mirror belt set temperature 120 ° C .; mirror belt pressure 1.4 MPa; take-up speed 5.6 m / min.

(A3) A biaxially stretched polyethylene terephthalate film “Diafoil (trade name)” manufactured by Mitsubishi Plastics Co., Ltd., having a thickness of 250 μm.

(A4) Sumitomo Chemical Co., Ltd. acrylic resin film “Technoloy (trade name)”, thickness 250 μm.

(A5) Using (β-1) above, a 50 mm extruder (with a W flight screw of L / D = 29, CR = 1.86); a T die having a die width of 680 mm; melting with a mirror roll and a mirror belt A film having a thickness of 250 μm was obtained using an apparatus equipped with a drawing winder equipped with a mechanism for pressing the film. At this time, the setting conditions of the extruder are C1 / C2 / C3 / AD = 280/300/320/320 ° C .; T die setting temperature 320 ° C .; T die lip opening 0.5 mm; Set temperature 140 ° C .; mirror belt set temperature 120 ° C .; mirror belt pressure 1.4 MPa; take-up speed 5.6 m / min.

Example 1
Production of hard coat laminate:
Corona discharge treatment was performed on both surfaces of the above (a1) under the conditions of a processing amount of 167 W · min / m ² (discharge power 500 W, discharge electrode length 1 m, line speed 3 m / min). The wetness index on both sides was 64 mN / m. Subsequently, the above-mentioned (γ-1) is applied to the surface on the α1 layer side as a touch surface side hard coat layer forming coating using a die type coating apparatus so that the thickness after curing is 25 μm. Applying the above (γ-2) as a printing surface side hard coat layer-forming coating on the α2 layer side surface using a die type coating apparatus so that the thickness after curing is 25 μm; A hard coat laminate was obtained. About the obtained hard-coat laminated body, evaluation of said (1)-(4) was performed.

Step (A):
The above (δ-1) was temporarily pasted on both surfaces of the hard coat laminate obtained above.

Step (B):
From the laminate of the support and the hard coat laminate obtained as described above, an article with a support having a shape as shown in FIG. 1 in a plan view was cut out using a router machine that automatically controlled by a computer. The mill used at this time was a four-blade made of cemented carbide with a rounded tip at the tip of the cylinder, with a nick, and the blade diameter was appropriately selected according to the machining location.

Step (C):
The article with the support obtained above was irradiated with 100 mJ / cm ^{2 of} ultraviolet rays using a high-pressure mercury lamp as a light source. The adhesive strength between the support and the article after irradiation was 0.5 N / 2.5 cm, and the support could be easily peeled and removed without causing any problems with the article. Moreover, about said obtained article, evaluation of said (5)-(9) was performed. The results are shown in Table 2.

Comparative Example 1
All were performed in the same manner as in Example 1 except that the ultraviolet irradiation in the step (C) was not performed. At this time, the adhesive strength between the support and the article was 3.8 N / 2.5 cm, and fine cracks were visually observed in several parts of the hard coat layer. Therefore, the evaluation of the above (5) to (9) was omitted. The results are shown in Table 2.

Example 2
The same procedure as in Example 1 was carried out except that (δ-2) was used instead of (δ-1) as the support. The adhesive strength between the support and the article after irradiation was 2.0 N / 2.5 cm. When the support was peeled and removed from the article, although it was not visually recognized, it was recognized that slight peeling marks that could be recognized by a loupe (magnification 10 times) were generated. Moreover, about said obtained article, evaluation of said (5)-(9) was performed. The results are shown in Table 2.

Example 3
The same procedure as in Example 2 was performed except that the irradiation dose in the step (C) was changed to 100 mJ / cm ² and changed to 200 mJ / cm ² . The adhesive strength between the support and the article after irradiation was 1.5 N / 2.5 cm, and the support could be easily peeled and removed without causing any problems with the article. Moreover, about said obtained article, evaluation of said (5)-(9) was performed. The results are shown in Table 2.

Comparative Example 2
All were performed in the same manner as in Example 2 except that the ultraviolet irradiation in the step (C) was not performed. At this time, the adhesive strength between the support and the article was 11.3 N / 2.5 cm, and cracks were visually observed in several parts of the hard coat layer. Therefore, the evaluation of the above (5) to (9) was omitted. The results are shown in Table 2.

Example 4
The above (γ-3) is used instead of the above (γ-1) as the hard coat layer forming paint on the touch surface side, and the above (γ-2) is used as the hard coat layer forming paint on the printing surface side. The procedure was the same as in Example 1 except that (γ-4) was used and the thickness after curing was 30 μm. The adhesive strength between the support and the article after irradiation was 0.6 N / 2.5 cm, and the support could be easily peeled and removed without causing any problems with the article. Moreover, about said obtained article, evaluation of said (5)-(9) was performed. The results are shown in Table 2.

Example 5
In the step (B), everything was performed in the same manner as in Example 1 except that a carbon dioxide gas (CO ₂ ) laser having a wavelength of 9.3 μm was used instead of the router processing machine. The adhesive strength between the support and the article after irradiation was 0.5 N / 2.5 cm, and the support could be easily peeled and removed without causing any problems with the article. Moreover, about said obtained article, evaluation of said (5)-(9) was performed. The results are shown in Table 3. In addition, (5) In the evaluation of the state of the curved cutting line, slight yellowing was observed on the end face.

Example 6
In the step (B), everything was carried out in the same manner as in Example 1 except that a spherical tip type mill was used instead of the cylindrical round shape. The adhesive strength between the support and the article after irradiation was 0.5 N / 2.5 cm, and the support could be easily peeled and removed without causing any problems with the article. Moreover, about said obtained article, evaluation of said (5)-(9) was performed. The results are shown in Table 3.

Example 7
The same procedure as in Example 1 was performed except that (a2) was used instead of (a1). The adhesive strength between the support and the article after irradiation was 0.5 N / 2.5 cm, and the support could be easily peeled and removed without causing any problems with the article. Moreover, about said obtained article, evaluation of said (5)-(9) was performed. The results are shown in Table 3.

Example 8
The same procedure as in Example 1 was performed except that (a3) was used instead of (a1). The adhesive strength between the support and the article after irradiation was 0.5 N / 2.5 cm, and the support could be easily peeled and removed without causing any problems with the article. Moreover, about said obtained article, evaluation of said (5)-(9) was performed. The linear expansion coefficient was not measurable due to significant shrinkage of the article. The results are shown in Table 3.

Example 9
The same procedure as in Example 1 was performed except that (a4) was used instead of (a1). The adhesive strength between the support and the article after irradiation was 0.6 N / 2.5 cm, and the support could be easily peeled and removed without causing any problems with the article. Moreover, about said obtained article, evaluation of said (5)-(9) was performed. The results are shown in Table 3.

Example 10
The same procedure as in Example 1 was performed except that (a5) was used instead of (a1). The adhesive strength between the support and the article after irradiation was 0.5 N / 2.5 cm, and the support could be easily peeled and removed without causing any problems with the article. Moreover, about said obtained article, evaluation of said (5)-(9) was performed. The results are shown in Table 3.

The production method of the present invention is excellent in transparency, surface hardness, scratch resistance, bending resistance, surface smoothness, and appearance, without causing a defective phenomenon such as cracking, and the touch panel display face plate and transparent conductivity. An article made of a hard coat laminate, which can be suitably used as a substrate, was obtained. In particular, in Examples 1 to 7, which are examples of the tenth invention of the present invention, articles excellent in heat resistance and dimensional stability are obtained. On the other hand, in Comparative Examples 1 and 2, since the step (C) of the production method of the present invention was lacking and the adhesive strength was high, defects such as cracks in the hard coat occurred.

It is a top view which shows an example of the articles | goods of this invention. It is a conceptual diagram which shows an example of the mill whose front-end | tip shape of a blade edge | tip is a cylindrical round shape. It is a conceptual diagram which shows an example of the mill whose tip shape of a blade edge | tip is a tip spherical type. It is a conceptual diagram which shows an example of the mill where the front-end | tip shape of the blade edge | tip is a front-end | tip spherical shape and was nicked. It is a figure explaining a curvature radius. 1 is a conceptual diagram of a coextrusion film forming apparatus used in Example 1. FIG.

1: Circular cutting hole with a radius of 0.1 mm 2: Cutting hole with both ends having a radius of curvature of 0.5 mm 3: Corner portion with a radius of curvature of 10 mm 4: Mill blade diameter 5: Mill blade length 6: Mill nick 7 : Extruder 1
8: Extruder 2
9: Co-extrusion T die of 2 types, 3 layers, multi-manifold system 10: Molten film 11: Mirror roll 12: Mirror belt 13: A pair of belt rollers

Claims (13)

In order from the outermost layer side, a method for producing an article comprising a hard coat laminate having a hard coat layer and a transparent resin film layer,
(A) a step of temporarily attaching a support having an adhesive layer on at least one surface and the hard coat laminate;
(B) A step of cutting out the article made of the hard coat laminate using at least one processing method selected from the group consisting of router processing, water jet processing, laser processing, and punching processing;
(C) using at least one selected from the group consisting of heat and active energy rays, and reducing the adhesive strength between the support and the article to 2 N / 2.5 cm or less;
Including methods.
The method according to claim 1, wherein router processing is used in the step (B).
The method according to claim 2, wherein the milling is performed using a mill whose tip shape is a cylindrical round shape or a tip sphere shape.
4. The method according to claim 2, wherein the mill is a nicked mill.
The method according to any one of claims 2 to 4, wherein a material of a cutting edge of the mill is a cemented carbide.
The method according to any one of claims 1 to 5, wherein the hard coat laminate satisfies the following property (A).
(A) The pencil hardness of at least one surface is 7H or more.
The method according to any one of claims 1 to 6, wherein the hard coat laminate satisfies the following characteristics (b) and (c).
(B) Total light transmittance of 90% or more.
(C) Haze 2.0% or less.
The method according to claim 1, wherein the hard coat laminate satisfies the following characteristics (d).
(D) The minimum bending radius is 40 mm or less.
The method according to claim 1, wherein the article has a curved cutting line having a radius of curvature of 0.1 to 20 mm in a plan view thereof.
The said hard-coat laminated body has a hard-coat layer (H) and a poly (meth) acrylimide-type resin layer ((alpha)) in an order from the outermost layer side, The any one of Claims 1-9 characterized by the above-mentioned. The method described in 1.
The hard coat laminate is in order from the outermost layer side,
First hard coat layer (H1);
Poly (meth) acrylimide resin layer (α);
The method according to any one of claims 1 to 10, further comprising a second hard coat layer (H2).
The hard coat laminate is in order from the outermost layer side,
First hard coat layer (H1);
First poly (meth) acrylimide resin layer (α1);
Aromatic polycarbonate-based resin layer (β);
Second poly (meth) acrylimide resin layer (α2);
A second hard coat layer (H2);
The method according to claim 1, wherein the α1, β, and α2 layers are directly laminated in this order.
A method of manufacturing a touch panel member,
A step of producing an article comprising a hard coat laminate having a hard coat layer and a transparent resin film layer by the method according to any one of claims 1 to 12; and
Using the article obtained in the above step;
Including methods.

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