JP2008133349A - Method for producing adhesive film with hard coat, and adhesive film with hard coat - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an adhesive film with a hard coat in excellent productivity by which the hard coat layer can be formed without using a base material film, the whole thickness of the adhesive film with the hard coat can be thinned, and a lubricant reducing optical characteristics such as transparency is not required to be contained in the hard coat layer; and to provide the adhesive film with the hard coat. <P>SOLUTION: The method for producing the adhesive film with the hard coat includes coating a resin layer A for forming an adhesive layer having ≥1 ball tack (by a slope type ball-tack measuring method based on JIS Z0237 at 30° tilt angle) at normal temperature by energy ray curing, and a resin layer B for forming the hard coat layer having 0 ball tack at normal temperature by energy ray curing in order so as to form a multilayer on one surface of a separator 15 having separable properties, and simultaneously curing the resin layer A and the resin layer B by irradiating them with the energy rays to simultaneously form the adhesive film having the adhesive layer 14 laminated on one surface of the hard coat layers 12 and 13. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing an adhesive film with a hard coat and an adhesive film with a hard coat.

  Generally, an adhesive film with a hard coat is provided with a pressure-sensitive adhesive layer made of an acrylic or rubber-based solvent-type pressure-sensitive adhesive, an emulsion-type pressure-sensitive adhesive, or a hot-melt pressure-sensitive adhesive on one side of a base film made of various films. A hard coat layer is provided on the surface opposite to the adhesive side of the base film. The product form is a form in which a separator such as a release film or release paper is bonded to the pressure-sensitive adhesive surface, or a release treatment is applied to the hard coat layer of the base film and the tape is wound up into a tape shape. Has been. For the production of hard-coated adhesive films, the adhesive is directly applied to the hard-coated substrate film, dried and cured, and then the separator is attached to the adhesive material surface. The adhesive is applied to the release-treated surface of the separator and dried. A method is used in which a base film that has been hard-coated on an adhesive is bonded after being cured.

In recent years, for example, in hard-coated adhesive films and protective films for displays, in order to improve yield and reduce costs, if there is a problem with the protective film or panel, separate the panel and protective film, Recycling of protective films or panels that are free from defects is being carried out. In addition, when disposing industrial products using hard-coated adhesive films, it is necessary to disassemble the products when disposing of industrial products and to dispose of the components separately for each type of material. There is a need for separation from the adherend and separation. For this reason, there is a demand for reworkability and correction workability of the application position for the hard-coated pressure-sensitive adhesive film, ease of peeling at the time of disposal, and further, the adhesive residue ( It is required that the phenomenon that the pressure-sensitive adhesive remains on the adherend surface does not occur. However, the adhesive film with a hard coat by the conventional manufacturing method has a problem that the adhesive force of the adhesive layer to the hard-coated substrate film is insufficient, and the adhesive residue is generated when the adhesive force to the adherend is strong. There was sometimes.
Similar to the problem of adhesive residue on the adherend, there is a similar requirement for the material coated on the surface opposite to the surface on which the adhesive layer of the adhesive film with hard coat is formed. For example, if an antistatic layer is coated on the hard coat layer, the adhesion and anchorage with the hard coat layer may be poor in some cases, and if the surface is rubbed, the coating layer may be removed or the hard coat layer may be attached. When the adhesive film is bent or cut, delamination may occur, causing problems.

  On the other hand, regarding the problem of waste, it is also required to reduce the overall thickness including the hard coat layer from the viewpoint of volume reduction when the adhesive film with hard coat becomes waste. However, in the conventional manufacturing method, since the base film is hard-coated, if the thickness of the base film decreases, the tension applied to the base film during processing in the adhesive coating / drying device is reduced. In order to prevent wrinkling and kinking of the base film, it is actually difficult to apply the adhesive layer thicker than the thickness of the base film. In addition, in the method of laminating a hard-coated base film after applying an adhesive on a separator, if the base film is thin, wrinkles and floats are likely to occur when the hard-coated base film is pasted. There's a problem.

  Furthermore, in the conventional technique, the method of applying the adhesive to the base film that has been hard-coated, if the thickness of the base film for hard coating does not have a thickness that can be wound around a roll, There is a problem that it cannot be processed. In addition, the base film itself for hard coating is added with a lubricant such as kaolin, calcium carbonate, colloidal silica, etc. in order to avoid problems such as wrinkles and scratches due to friction when winding into a roll. The surface of the base film for hard coating is slippery by a method such as precipitating a part or all of the catalyst to be used, or providing a fine particle layer or coating layer on the surface (for example, see Patent Documents 1 and 2). So that it can be smoothly wound into a roll. However, considering the application to the optical field, even if a highly transparent resin is used for the base film itself for hard coating, techniques such as addition of a lubricant, precipitation of a catalyst, formation of irregularities on the surface, etc. When employed, the optical properties (transparency, etc.) of the base film for hard coating are considered inferior.

Moreover, in the prior art, in the manufacturing method of the hard coat film formed using an energy ray curable resin for both the hard coat layer and the pressure-sensitive adhesive layer, the hard coat layer and the pressure-sensitive adhesive layer are coated on the base film. Had to be coated separately on both sides of the substrate film. Or the special manufacturing apparatus which coats simultaneously on both surfaces of a base film was required. Further, in optical characteristics, it has been difficult to reduce haze and increase transmittance due to the influence of a lubricant contained in the base film. Furthermore, the adhesion between the base film, the hard coat layer, and the pressure-sensitive adhesive layer may be poor, and there has been a problem such as delamination during the work of peeling off and pasting the pasted hard coat film again.
In Patent Document 3, a coating solution for forming a buffer layer is coated on one surface of a base film and cured with energy rays, and then a hard coat layer is formed on the surface of the cured buffer layer. Although a hard coat film coated with a liquid and cured with energy rays has been disclosed, since the substrate film is used, the above-described problems related to the prior art have not been completely solved.

Thus, in the prior art, the above-mentioned problems have occurred because the hard coat layer is laminated and coated using the base film.
JP-A-5-70612 JP 2003-119305 A JP-A-11-300873

  The present invention has been made in view of the above circumstances, a hard coat layer can be formed without using a base film, the entire thickness of the adhesive film with a hard coat can be reduced, and in the hard coat layer It is an object of the present invention to provide a method for producing a pressure-sensitive adhesive film with a hard coat and a pressure-sensitive adhesive film with a hard coat, which do not need to contain a lubricant that reduces optical properties such as transparency, and has excellent productivity.

  In order to solve the above-mentioned problem, the present invention was measured at an inclination angle of 30 degrees on one surface of a separator having releasability by an inclined ball tack measurement method according to JIS Z0237 at room temperature by energy ray curing. A pressure-sensitive adhesive layer forming resin layer A having a ball tack of 1 or more and a ball tack measured at an inclination angle of 30 degrees by an inclined ball tack measurement method in accordance with JIS Z0237 at normal temperature by energy ray curing are 0 After the multilayer coating of the resin layer B for forming the hard coat layer is performed in order, the resin layer A and the resin layer B are simultaneously cured by irradiating energy rays, whereby an adhesive is applied to one surface of the hard coat layer. Provided is a method for producing a hard-coated pressure-sensitive adhesive film, wherein a pressure-sensitive adhesive film in which layers are laminated is formed at a time.

The resin layer A and the resin layer B are preferably made of a solventless energy ray-curable composition.
The resin layer B is preferably composed of at least two multilayer-coated resin layers, and has a hard coat property of H or more in a pencil hardness test according to JIS K5600-5-4,5. Further, an antireflection layer may be laminated on the resin layer B. Further, an antireflection layer and an antifouling layer as the outermost layer may be laminated on the resin layer B.

The separator is one selected from the group of flexible release bodies such as synthetic resin films, metal foils, release papers, and the like even after the resin layer A and the resin layer B are simultaneously cured. A separator may be bonded to the resin layer A.
Further, the separator is one selected from the group of non-flexible peeled bodies such as a synthetic resin plate, a metal plate, and a glass plate, and the resin layer A and the resin layer B are simultaneously cured. The separator may be peeled off from the resin layer A later.
Moreover, this invention provides the adhesive film with a hard coat obtained by said manufacturing method, and the adhesive layer was laminated | stacked on the one surface of the hard-coat layer.

According to the present invention, the adhesive layer forming resin layer A having a ball tack of 1 or more and the hard coat layer forming resin layer B having a ball tack of 0 are simultaneously polymerized and cured to form an adhesive layer. And the hard coat layer are formed at the same time, and the following effects are obtained.
(1) Adhesion is improved due to easy formation of a chemical bond between the hard coat layer and the adhesive layer and the anchoring effect of the adhesive layer on the hard coat layer. Even when affixed to a kimono, the problem of adhesive residue is less likely to occur.
(2) A hard coat layer can be formed without using a base film, and the thickness of the hard coat layer and the pressure-sensitive adhesive can be freely set. There is no problem. Therefore, the adhesive film with a hard coat whose whole thickness is thinner than before can be manufactured.
(3) Since there is no step of winding only the hard coat layer into a roll with a single film during the manufacturing process, it is not necessary to mix a component for imparting slipperiness such as a lubricant to the hard coat layer. Therefore, the adhesive film with a hard coat which was excellent in optical characteristics, such as transparency, can be manufactured.

  When a solventless energy ray curable resin composition is used as the resin layer A for forming the adhesive layer and the resin layer B for forming the hard coat layer, no solvent is used, so the working environment is deteriorated and air pollution is caused. There is almost no generation of volatile organic compounds (VOC) that lead to. In addition, since aging (curing) period and drying are not required, the time required for production is shortened, and it can be manufactured with compact equipment.

The present invention will be described below based on the best mode.
The method for producing a pressure-sensitive adhesive film with a hard coat according to the present invention comprises a resin layer A for forming a pressure-sensitive adhesive layer on one surface of a separator having releasability and having a ball tack at room temperature of 1 or more by energy ray curing; The resin layer B for forming a hard coat layer having a ball tack of 0 at room temperature by energy ray curing is sequentially multilayer coated, and then the resin layer A and the resin layer B are simultaneously cured by irradiating energy rays. Thus, an adhesive film in which an adhesive layer is laminated on one surface of a hard coat layer is formed at a time.
In the present invention, the ball tack is measured at an inclination angle of 30 degrees by an inclined ball tack measurement method according to JIS Z0237.

  Here, as a method of forming the resin layer A for forming the adhesive layer and the resin layer B for forming the hard coat layer, multilayer coating on the separator can be preferably employed. In this case, if at least one layer each of the resin layer A and the resin layer B is coated on the separator and cured each time, the structure of the conventional general adhesive film is obtained. The number and thickness of the resin layer A for forming the pressure-sensitive adhesive layer and the resin layer B for forming the hard coat layer are not limited as long as the entire multilayer coating is flexible and depends on the function required. The resin layer A for forming the pressure-sensitive adhesive layer and / or the resin layer B for forming the hard coat layer can be made into a plurality of layers. The resin layer B is composed of at least two multilayer-coated resin layers, and the outermost layer (the surface opposite to the surface on which the adhesive layer forming resin layer A is formed) has a hard coat property after curing. You can also.

As a separator, 1 type selected from the group of the peeling body which has flexibility, such as a synthetic resin film, metal foil, and release paper, can be used. In this case, the pressure-sensitive adhesive film with a hard coat can be wound into a roll while the separator is bonded without peeling off the separator. Therefore, even after the resin layer A and the resin layer B are simultaneously cured, the separator It can be formed by bonding with the resin layer A.
Examples of the flexible release body include polycarbonate film, polyarylate film, polyethersulfone film, polysulfone film, polyester film, polystyrene film, polyolefin film, norbornene film, phenoxyether type polymer film, and organic permeation resistance. A release film having a release property with a silicone release agent or the like applied to a single-layer or multilayer plastic film such as a gas-resistant film and having a release property at least on one side; Release film having a releasability; a film having a releasability such as a fluorine-based resin film or a certain type of polyolefin film; a film formed by internally adding a release agent.

  Moreover, 1 type selected from the group of the peeling body which does not have flexibility, such as a synthetic resin plate, a metal plate, and a glass plate, can also be used for a separator. In this case, after the resin layer A and the resin layer B are simultaneously cured, the separator is peeled off from the cured resin layer A to obtain a hard coat pressure-sensitive adhesive film in which a pressure-sensitive adhesive layer is laminated on the hard coat layer. It can be manufactured and wound up as it is. In addition, it is preferable that the surface of the separator is subjected to a peeling treatment with a silicone-based release agent or the like, a mirror polishing finish by mechanical polishing or chemical polishing, or the like, so that at least one surface has peelability.

  Although the thickness of a separator is not specifically limited, When winding a separator in the state which bonded the adhesive film together, it is 5-500 micrometers normally, Preferably it is 10-100 micrometers in many cases. The material of a separator shall be selected according to the use application (adhesive peel strength, the presence or absence of a separator) of the adhesive to be used or the adhesive film with a hard coat.

The pressure-sensitive adhesive layer-forming resin layer A having a ball tack of 1 or more can be formed by coating a pressure-sensitive adhesive layer-forming resin composition containing an energy ray-curable compound that is cured by energy ray irradiation. . Examples of the energy rays used for curing the resin layer A include heating and active energy rays (ultraviolet rays, electron beams, and in some cases, visible rays).
When curing by heating, it is usual to blend about 0.1 to 5% by weight of a polymerization initiator in advance with respect to the entire resin composition for forming the pressure-sensitive adhesive layer. As the polymerization initiator, an organic peroxide-based or diazonium-based polymerization initiator is preferably used.
When curing is performed by irradiation with ultraviolet rays or visible rays, it is usual to blend about 0.1 to 10% by weight of a polymerization initiator in advance with respect to the entire resin composition for forming the pressure-sensitive adhesive layer. However, it may not be necessary when using a cationic or anionic polymerization method. In the case of irradiation with active energy rays, it is possible to complete curing by performing a heat treatment as necessary after the irradiation, and conversely, the energy treatment may be performed after the heat treatment. You may combine the above energy beam irradiation.

The photopolymerization initiator used in the case of curing by irradiation with ultraviolet rays or visible rays is not particularly limited. Examples include diethylthioxanthone, acetophenone diethyl ketal, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, among which benzyl dimethyl ketal and 1-hydroxycyclohexyl phenyl. A ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, or the like is preferably used.
As the cationic photopolymerization initiator, initiators such as onium salt, tri (substituted) phenylsulfonium, diazosulfone and iodonium are preferably used. As the anionic photopolymerization initiator, an organometallic initiator such as alkyl lithium is preferably used.
The composition of the resin composition for forming the pressure-sensitive adhesive layer is preferably adjusted so that the glass transition point of the film after curing with energy rays is 20 ° C. or less.

The resin composition for forming the pressure-sensitive adhesive layer is preferably a fluid, solventless, high-viscosity adhesive resin composition. In particular, an adhesive grade acrylic copolymer obtained by copolymerizing a monomer component that gives a soft segment and a monomer component that gives a hard segment (and if necessary, a functional group-containing monomer component or a polyfunctional (meth) acrylate component). What uses a polymer as an essential component is used suitably.
In the present specification, “(meth) acrylate” means “acrylate and / or methacrylate”.

  In the pressure-sensitive adhesive grade acrylic copolymer, a monomer component that gives a soft segment when polymerized is an alkyl acrylate having an alkyl group with 4 or more carbon atoms (n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl). Acrylate, etc.), alkyl methacrylates having 6 or more carbon atoms in the alkyl group (n-hexyl methacrylate, 2-ethylhexyl methacrylate, etc.) and the like. These monomers may be used independently and may be used in combination of 2 or more type.

  Monomer components that give hard segments include alkyl acrylates having 1 to 3 carbon atoms in the alkyl group (such as methyl acrylate), alkyl methacrylates having 1 to 5 carbon atoms in the alkyl group (such as methyl methacrylate), vinyl acetate, and styrene. Is mentioned. These monomers may be used independently and may be used in combination of 2 or more type.

  As functional group-containing monomer components, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, glycidyl (meth) acrylate, N-methylolacrylamide, 2-hydroxyethyl acrylate , Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and the like. These monomers may be used independently and may be used in combination of 2 or more type.

  As polyfunctional (meth) acrylate components, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, 1,6-hexanediol, neopentyl glycol Di-, tri- or poly (meth) acrylates of polyhydric alcohols such as trimethylolpropane, glycerin and pentaerythritol; hydroxyalkyl (meth) acrylates and the like. These monomers may be used independently and may be used in combination of 2 or more type.

The pressure-sensitive adhesive grade acrylic resin composition includes the above-mentioned acrylic copolymer, the monomer that gives the soft segment, the monomer that gives the hard segment, the monomer containing the functional group, and the polyfunctional (meth) acrylate. It is preferable to add in a monomer form. These monomers act as a plasticizer for the acrylic copolymer during film formation to impart fluidity, and then cure and polymerize by irradiation with energy rays. A relatively low molecular weight oligomer or a general plasticizer can be used together with or in place of such a monomer.
In addition, there is a formulation in which the above acrylate monomer is added in order to lower the viscosity of the high viscosity oligomer resin. Specific examples of the oligomer include urethane acrylates such as polyesters and polycarbonates, polyester acrylates, epoxy acrylates, polyethylene glycol diacrylates, commercially available oligoester acrylates, methacrylates similar to the above, and the like. These oligomers may be used alone or in combination of two or more.

  In addition to the above-mentioned acrylic polymer as an essential component, the high-viscosity adhesive resin composition includes urethane, polycarbonate, polyester, acrylic urethane, rubber, vinyl, and silicone adhesives. An agent grade resin composition can also be used.

  The viscosity of the resin composition for forming the pressure-sensitive adhesive layer is suitably about 20 to 100000 cps / 20 ° C, preferably 20 to 80000 cps / 20 ° C, more preferably 20 to 12000 cps / 20 ° C.

The resin layer B for forming a hard coat layer can be formed by coating a resin composition for forming a hard coat layer. The resin composition for forming the hard coat layer is preferably a fluid, solventless energy ray-curable composition. This energy ray-curable composition contains an energy ray-curable compound that is cured by energy rays as an essential component, and a resin that has a ball tack after curing of 0 is used.
Examples of energy rays used for curing include heating and active energy rays (ultraviolet rays, electron beams, and in some cases, visible rays).
In the case of curing by heating, it is usual to blend about 0.1 to 5% by weight of a polymerization initiator in advance with respect to the entire resin composition for forming the hard coat layer. As the polymerization initiator, an organic peroxide-based or diazonium-based polymerization initiator is preferably used.
When curing is performed by irradiation with ultraviolet rays or visible rays, it is usual to blend about 0.1 to 10% by weight of a polymerization initiator in advance with respect to the entire resin composition for forming a hard coat layer. However, it may not be necessary when using a cationic or anionic polymerization method. In the case of irradiation with active energy rays, it is possible to complete curing by performing a heat treatment as necessary after the irradiation, and conversely, the energy treatment may be performed after the heat treatment. You may combine the above energy beam irradiation.

The photopolymerization initiator used in the case of curing by irradiation with ultraviolet rays or visible rays is not particularly limited. Examples include diethylthioxanthone, acetophenone diethyl ketal, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, among which benzyl dimethyl ketal and 1-hydroxycyclohexyl phenyl. A ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, or the like is preferably used.
As the cationic photopolymerization initiator, initiators such as onium salt, tri (substituted) phenylsulfonium, diazosulfone and iodonium are preferably used. As the anionic photopolymerization initiator, an organometallic initiator such as alkyl lithium is preferably used.
The blending of the energy beam curable composition for forming the hard coat layer is preferably adjusted so that the ball tack after the energy beam curing becomes zero.

The hard coat layer of the present invention may be any resin as long as it is transparent in a cured state and has sufficient hardness, but an acrylic resin, a urethane resin, a melamine resin, an organic silicate compound, Among silicone resins or metal oxides, preferred examples include resins that are cured by actinic rays such as acrylate, vinyl, urethane acrylate, ester acrylate, and epoxy acrylate monomers and oligomers. In particular, silicone resins and acrylic resins are preferable in terms of hardness and durability, and acrylic resins, particularly active ray curable acrylic resins, in terms of curability, flexibility, and productivity. Those consisting of are preferred. The thickness of the hard coat layer is difficult to measure from actually fabricated kind but is within the range of coating amount of 0.1 to 30 g / ^{m 2,} the range preferably of 1 to 15 g / ^{m 2} Is within. When the coating amount is less than 1 g / m ² , hardness such as scratch resistance may be inferior. On the other hand, when the coating amount exceeds 30 g / m ² , haze increases and curling tends to occur. In addition, the cured film tends to crack due to stress such as bending. Moreover, you may provide printing layers, such as a pattern, in the outermost layer of a hard-coat layer in the range which does not impair the effect of this invention.

  Commercially available acrylic cured paints include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam” series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol” series, etc.), Shin Nakamura Co., Ltd. ( (Product name "NK Ester" series, etc.), Dainippon Ink and Chemicals Co., Ltd .; (Product name "UNIDIC" series, etc.), Toa Gosei Chemical Industry Co., Ltd. (product name "Aronix" series, etc.), Nippon Oil & Fats ( (Trade name “Blemmer” series, etc.), Nippon Kayaku Co., Ltd .; (trade name “KAYARAD” series, etc.), Kyoeisha Chemical Co., Ltd .; (trade names “light ester” series, “light acrylate” series) Etc.) can be used.

  Specific examples of acrylic oligomers, reactive diluents, photopolymerization initiators, photosensitizers, crosslinking devices, etc. are from Shinzo Yamashita, Tosuke Kaneko, “Crosslinking Agent Handbook”, Taiseisha published in 1981, page 267. Reference can be made to pages 275 and 562 to 593, but the present invention is not limited to these. Commercially available multi-functional acrylic UV curable paints such as Mitsubishi Rayon Co., Ltd., Fujikura Kasei Co., Ltd., Dainichi Seika Kogyo Co., Ltd., Dainippon Ink Chemical Co., Ltd., Toa Gosei Chemical Co., Ltd., Nitto Kasei Co., Ltd. Products such as Co., Ltd. and Nippon Kayaku Co., Ltd. can be used.

In the present invention, as a modifier for the hard coat layer, a coating property improver, an antifoaming agent, a thickener, an antistatic agent, inorganic particles, organic particles, an organic lubricant, an organic polymer compound, an ultraviolet ray, Absorbers, light stabilizers, dyes, pigments or stabilizers can be used, and these are used as a composition component of the coating layer constituting the hard coat layer within a range that does not impair the reaction by active rays,
The properties of the hard coat layer can be improved depending on the application.

As a means for applying a coating (coating liquid) containing a composition for forming a hard coat layer,
Various coating methods such as reverse coating, gravure coating, rod coating, bar coating, die coating, or spray coating can be used.

In the method for producing a pressure-sensitive adhesive film of the present invention, a resin layer A for forming a pressure-sensitive adhesive layer and a resin layer B for forming a hard coat layer are multilayer coated on a separator or other object to be coated and irradiated with energy rays. Thus, the resin layer A for forming the adhesive layer and the resin layer B for forming the hard coat layer are simultaneously cured. Moreover, when irradiating an energy ray, the separator etc. which can permeate | transmit an energy ray can be covered on the coating layer as needed.
Thereby, the adhesive film by which the adhesive layer was laminated | stacked on the one surface of the hard-coat layer can be formed at once. The pressure-sensitive adhesive film thus produced preferably has a ball tack at normal temperature after curing of the hard coat layer of 0, and a ball tack at normal temperature after curing of the pressure-sensitive adhesive layer of 1 or more. Thereby, the adhesive film which has an adhesive layer which expresses adhesiveness at normal temperature, and a hard-coat layer which does not express adhesiveness at normal temperature can be obtained.

  The viscosity of the resin composition for forming the hard coat layer may be the same as or different from that of the resin composition for forming the adhesive layer. The hard coat layer and the pressure-sensitive adhesive layer can be obtained in a lump by coating each layer and irradiating it with energy rays before the layers are completely compatible. It is considered that it is better to first coat a resin composition having a high viscosity and then coat a resin composition having a low viscosity because an existing apparatus can be used in an actual production process. Also, before coating a low-viscosity resin composition on a support such as a separator, a method of coating after slightly increasing the viscosity by irradiating energy rays that do not completely cure, or after coating with a low viscosity Resin composition to be coated first, such as by applying a layer of the next low viscosity composition after the viscosity is increased by irradiating energy rays that do not harden, and then completely curing with energy rays. On the other hand, it is effective in an actual production process to increase the viscosity by some method and then coat the next resin composition.

As a manufacturing method, although the following method can be considered, it is not limited.
Irradiation with active energy rays (ultraviolet rays, electron beams, and in some cases visible light) in a state where oxygen in the energy ray irradiation atmosphere is excluded as much as possible, and a production method (1) for curing the resin, and in the active energy ray irradiation atmosphere However, there is a manufacturing method (2) in which oxygen is not in contact with the energy curable resin and irradiation with active energy rays is performed.

  Specifically, the production method (1) comprises forming a layer structure of separator (1) / resin layer for forming an adhesive layer (A) / resin layer for forming a hard coat layer (B), and then active energy rays. The structure which manufactures the adhesive film which has a layer structure of separator (1) / adhesive layer (a) / hard-coat layer (b) after irradiation is considered. When the separator (2) is necessary as a process or product after irradiation with active energy rays, the separator (2) may be bonded before irradiation with active energy rays, and the separator (2) may be applied while irradiating with active energy rays. It may be pasted or in any order such as pasting the separator (2) after irradiation with active energy rays.

In the case of the production method (1), since the separator (2) is not bonded before the active energy ray irradiation, the active energy ray irradiation atmosphere is made of an inert gas such as nitrogen so as not to be insufficiently cured due to polymerization inhibition. It is necessary to replace with an atmosphere that does not cause polymerization inhibition. The term “polymerization inhibition” as used herein means that a radical that is easily absorbed by radicals such as oxygen is present in the atmosphere irradiated with active energy rays, so that radicals used for polymerization are taken and the polymerization reaction does not proceed. means. In particular, in the case of oxygen, nitrogen substitution or the like is often performed in order to suppress oxygen inhibition by oxygen radicals generated by irradiation with active energy rays.
In order to cure even if there is polymerization inhibition, it is known to add a large amount of expensive polymerization initiator, but the degradation product of the photopolymerization initiator remains as an impurity and the adhesive force changes, Nitrogen etc. because it is not effective in actual production due to problems such as glue remaining or transfer of decomposed products, or problems such as increased total irradiation amount of active energy rays and reduced processing speed It is necessary to perform substitution with.

Specifically, the production method (2) forms a layer structure of separator (1) / resin layer for forming an adhesive layer (A) / resin layer for forming a hard coat layer (B), and separator (2) Is bonded to the resin layer (B) for forming the hard coat layer, or after being bonded, by irradiating active energy rays, the separator (1) / adhesive layer (a) / hard coat layer (b The structure which manufactures the adhesive film which has a layer structure of) / separator (2) can be considered.
When the separator (2) is unnecessary as a process or product after irradiation with active energy rays, the separator (2) is peeled off after irradiation with energy rays to obtain a product.

By using the separator (2), it is possible to easily form an environment in which no substitution of nitrogen or the like is required and there is no polymerization inhibition, surface protection of the hard coat layer (b), hard coat layer (b) by transfer of the separator surface structure (b It is possible to increase the added value with an inexpensive device such as control of the surface shape). However, in order to paste the separator (2) neatly, it is preferable that the viscosity of the resin layer (A) for forming the pressure-sensitive adhesive layer and the resin layer (B) for forming the hard coat layer is higher.
Therefore, in the case of the resin layer (B) for forming a hard coat layer having a low viscosity, it is necessary to devise procedures such as pasting the separator (2) in a state where the viscosity is increased by slightly curing, After slightly curing in the state of the layer configuration of the separator (1) / resin layer for forming the adhesive layer (A) / resin layer for forming the hard coat layer (B), the separator (2) was bonded. It is considered that the combination of the production method (1) and the production method (2) online or offline, such as irradiation with active energy rays again and curing, is also effective in actual production.

Further, only the separator (1) / resin layer forming resin layer (A) is combined with the manufacturing method (1) or the separator (2), and once irradiated with active energy rays in the state of the manufacturing method (2), it is slightly cured. Then, the resin layer (B) for forming the hard coat layer is coated on the resin layer (A) for forming the adhesive layer, and the manufacturing method (2) is combined with the manufacturing method (1) or the separator (2). In the state of), various procedures can be considered for the laminating method, such as curing by irradiating active energy rays and curing the layers little by little and finally curing the whole.
Moreover, when there is little superposition | polymerization inhibition of oxygen radicals, such as hardening by heating, you may select either a manufacturing method (1) or a manufacturing method (2).
Further, the adhesive layer (b) on both sides of the hard coat layer (b) such as separator (1) / adhesive layer (a) / hard coat layer (b) / adhesive layer (a) / separator (2) The structure of the double-sided pressure-sensitive adhesive film having a) can also be produced by either one of the production method (1) and the production method (2) or a combination thereof.

  The separator (1) on the pressure-sensitive adhesive layer side is usually peeled and removed immediately before the pressure-sensitive adhesive film is attached to the adherend. The separator (2) on the hard coat layer side may be peeled and removed at the time when the necessity arises, and depending on the application, it may not be peeled off after the adhesive film is attached to the adherend. For example, in order to protect the adhesive film attached to the adherend, the separator (2) on the hard coat layer side can be left attached.

  In the case where the separators (1) and (2) are long films or sheets wound up in a roll shape, the produced pressure-sensitive adhesive film can be wound up again in a roll shape, and the production method is excellent in productivity. It becomes. In this case, as a manufacturing facility, a feeding device for feeding the wound-up separator (1), a resin layer A for forming an adhesive layer and a resin layer B for forming a hard coat layer are multilayer coated on the separator (1). A coater, a laminating roll for laminating the separator (2) on the multilayer coating, an energy ray irradiation device for curing the resin layer A for forming the adhesive layer and the resin layer B for forming the hard coat layer, an adhesive layer, and It can comprise by the winding apparatus which winds up the adhesive film in which the hard-coat layer hardened | cured.

  Conventionally, in the case of producing a pressure-sensitive adhesive film by applying a solvent-type pressure-sensitive adhesive to a film with a hard coat, a long dryer is required. However, according to the present invention, since a dryer is not required, The total equipment length up to the take-off device can be stored in a compact manner. Moreover, since drying and aging are not required, the time required for production can be shortened, productivity can be improved, and dust can be prevented from adhering to the product.

  In the present invention, the separator in which the resin layer A for forming the pressure-sensitive adhesive layer and the resin layer B for forming the hard coat layer are sequentially coated with a multilayer has flexibility such as a synthetic resin film, a metal foil, and release paper. It does not need to be a peeled body, for example, a metal plate (for example, a stainless steel plate), a glass plate, a synthetic resin plate, etc. that has been made peelable by, for example, peeling with silicone or mirror finishing by mechanical polishing or chemical polishing. A pressure-sensitive adhesive film with a hard coat having an adhesive layer and a hard coat layer can also be produced by using an exfoliant that does not have flexibility, and then applying a multilayer coating thereon followed by irradiation with energy rays and simultaneously curing. . In this case, after peeling off the adhesive film from the non-flexible peeled body, it may be bonded with a new flexible peeled body in order to protect the pressure-sensitive adhesive layer of the produced hard-coated pressure-sensitive adhesive film. Good. Moreover, you may stick the adhesive film peeled off from the peeling body which does not have flexibility to a to-be-adhered body as it is. Furthermore, the adhesive film peeled off from the peeling body which does not have flexibility can be wound up in roll shape as it is. By slitting the roll body to a predetermined width, it can be processed into an adhesive tape with a hard coat.

  The present invention may be configured such that an antireflection layer is laminated on the resin layer B (the surface opposite to the surface on which the adhesive layer forming resin layer A is formed). Here, the antireflection layer is for preventing reflection of visible light from the outside when the adhesive film with a hard coat is attached to an adherend for optical use. A thin film of a material having a lower refractive index than the resin layer B for forming the hard coat layer that supports the prevention layer, for example, a fluorine-containing organic compound having a polysiloxane structure is formed. In the case of multiple layers, a material having a higher refractive index than the resin layer B for forming the hard coat layer, for example, a vapor deposition thin film of titanium oxide, and a material having a lower refractive index than the resin layer B for forming the hard coat layer. For example, thin films of silicon oxide are alternately laminated. The formation method of such a metal oxide thin film is not particularly limited, and a thin film of zirconium oxide, ITO, silicon oxide, or the like can be formed by a sputtering method, a vacuum evaporation method, or a wet coating method.

Furthermore, it is preferable to have an antifouling layer on the resin layer B or the antireflection layer because it can be easily removed when it is prevented from being smudged or smudged with fingerprints. As an antifouling layer, it has a non-wetting property with respect to water and / or fats and oils, for example, the water-repellent coating which consists of a fluorine-type compound and a silicon-type compound is mentioned. Specific examples of the fluorine-based water-repellent paint include trade name OPTOOL (manufactured by Daikin), and examples of the silicon-based water-repellent paint include trade name Takata Quantum (manufactured by NOF Corporation). These water-repellent paints are applied thinly on the resin layer B and the antireflection layer so that the coating film thickness is about 1 to 50 nm. If the coating film thickness of the water-repellent coating is thicker than 50 nm, the effect of the antireflection layer or the like is adversely affected, which is not preferable.
In addition, for a water-repellent paint made of a fluorine compound or a silicon compound, a material that is cured by irradiation with energy rays may be used. In the case of providing an antifouling layer on the resin layer B, in order to improve the adhesion of the antifouling layer, an energy ray curable material may be coated on the resin B or the like and simultaneously cured with energy rays. preferable. Examples of the energy ray curable material include fluorine-containing polyfunctional (meth) acrylate compounds. Examples of the fluorine-containing polyfunctional (meth) acrylate compound include linear perfluoroalkylene di (meth) acrylate, perfluoropolyether di (meth) acrylate, perfluoropolyether tri (meth) acrylate, and perfluoropolyether. Examples include tetra (meth) acrylate.

As described above, according to the method for producing a pressure-sensitive adhesive film of the present invention, the multilayer-coated pressure-sensitive adhesive layer forming resin layer A and the hard coat layer forming resin layer B are simultaneously polymerized and cured by irradiation with energy rays. When the adhesive layer and the hard coat layer are formed at the same time, the adhesion of the adhesive layer to the hard coat layer is improved and the adhesive layer such as glass or metal plate has a strong adhesive force. However, when the adhesive film is peeled off from the adherend, the problem of adhesive residue hardly occurs.
Moreover, according to this invention, while being able to form a hard-coat layer, without using a base film, the thickness of a hard-coat layer and an adhesive can be set freely, and a manufacturing problem does not arise. Therefore, the thickness of the hard coat layer can be reduced, and an adhesive film with a hard coat having a thinner overall thickness than conventional ones can be produced.
Since there is no step of winding the hard coat layer alone in the manufacturing process, it is not necessary to mix a component for imparting slipperiness such as a lubricant to the hard coat layer. Therefore, the adhesive film with a hard coat which was excellent in optical characteristics, such as transparency, can be manufactured.

  When a solventless energy ray curable resin composition is used as the resin layer A for forming the adhesive layer and the resin layer B for forming the hard coat layer, since no solvent is used, work environment deterioration and air pollution There is little generation of connected volatile organic compounds (VOC). For this reason, the expense and space for installing the equipment which collect | recovers and processes VOC can be reduced. In addition, since aging (curing) period and drying are not required, the time required for production is shortened, and it can be manufactured with compact equipment.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Hereinafter, “parts” means parts by weight.

As evaluation items, VOC generation, ball tackiness, hard coat properties, hard coat adhesion, and cutting suitability were examined.
VOC generation was determined by whether or not an organic solvent was used in the paint to be used, and OK when not used and NG when used.
Ball tackiness was measured by an inclined ball tack measurement method (an inclination angle of 30 degrees) according to JIS Z0237.
Regarding the hard coat property, the surface rubbed with steel wool 5 times was less visually scratched than the PET film alone, and after confirming the hard coat layer surface, JIS K5600-5-4 from the hard coat layer surface side. A pencil hardness test according to 5 was performed.
Hard coat adhesion is the adhesion between the pressure-sensitive adhesive layer (a) and the hard coat layer (b), and the hard coat layer (b) and the hard coat layer (c). When evaluating reworkability, check that there is no peeling between each layer, and that optical properties, particularly transparency and reflection, are observed visually. If there is no change, OK, transparency drops or becomes cloudy The case where peeling occurred to such an extent that reflection occurred was defined as NG.
The cutting suitability is checked with a razor blade (manufactured by Feather Safety Razor Co., Ltd., product name FAS-10) to visually check whether the adhesive film does not pull the thread, and there is no threading. The case was OK, and the case with stringing was NG. Furthermore, the cross section of the interface cut with a razor blade was observed with a polarizing microscope, and it was confirmed whether a clear interface could be observed or a so-called inclined layer, and the correlation with the hard coat adhesion was examined.

(Example 1)
As an example of release films (1) and (2) which are release bodies having flexibility, a biaxially stretched polyethylene terephthalate film having a thickness of 38 μm and having a release treatment with a silicone release agent on one side was prepared.
In addition, as a fluid solventless adhesive resin composition (A) for forming the adhesive layer (a), 50 parts of a urethane acrylate oligomer having a benzene ring as a hard segment and an alkyl group as a repeating unit. A mixed liquid in which 50 parts of 2-ethylhexyl acrylate and 3 parts of a photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) were mixed was prepared.

Further, as the UV curable resin (B) for forming the hard coat layer (b), a urethane acrylate oligomer having a polycarbonate skeleton as a hard segment and an alkyl group in a repeating unit and a photopolymerization initiator (trade name: Irgacure 184, A mixed liquid in which 3 parts of Ciba Specialty Chemicals) were mixed was prepared.
Furthermore, an ultraviolet curable acrylic hard coat agent was prepared as the UV curable resin (C) for forming the hard coat layer (c).

The release film (1) is coated with three layers of the pressure-sensitive adhesive composition (A) for forming the pressure-sensitive adhesive layer (a), the UV curable resin (B), and the UV curable resin (C) at the same time. The release film (2) was pasted on these three coating layers so as not to contain bubbles. Specifically, the adhesive resin composition (A) is formed with an applicator with a gap of about 30 μm, and the UV curable resin (B) is formed with an applicator with a gap of about 70 μm. A UV curable resin (C) was formed with an applicator at a gap of about 80 μm.
The coating layer was cured by irradiating with ultraviolet rays under the conditions of an output of 120 W / cm, a lamp distance of 150 mm, and an integrated light amount of 600 mJ / cm ² . Thereby, as shown in FIG. 1, an adhesive film having a layer structure of release film (1) / adhesive layer (a) / hard coat layer (b) / hard coat layer (c) / release film (2) Obtained.

  Generation | occurrence | production of VOC from the produced film was OK in order not to use an organic solvent. The ball tack of the pressure-sensitive adhesive layer (a) was 3. Further, the ball tack of the hard coat layer (c) was 0. The hard coat property was 2H in the pencil hardness test. The hard coat adhesion was OK. The cutting suitability was also OK, a clear interface could not be confirmed, and it was estimated that it was a continuous layer.

(Example 2)
As a fluid, solventless, high-viscosity adhesive resin composition (A) for forming an adhesive layer (a), 90 parts of a urethane acrylate oligomer having a benzene ring as a hard segment and an alkyl group as a repeating unit A mixed solution was prepared by mixing 10 parts of 2-ethylhexyl acrylate and 3 parts of a photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals). Except for this adhesive resin composition (A), the same procedure as in Example 1 was followed, except for release film (1) / adhesive layer (a) / hard coat layer (b) / hard coat layer (c) / release film (2 ) Was obtained.

  Generation | occurrence | production of VOC from the produced film was OK in order not to use an organic solvent. The ball tack of the pressure-sensitive adhesive layer (a) was 1. Further, the ball tack of the hard coat layer (c) was 0. The hard coat property was 2H in the pencil hardness test. The hard coat adhesion was OK. The cutting suitability was also OK, a clear interface could not be confirmed, and it was estimated that it was a continuous layer.

(Example 3)
As a fluid solventless adhesive resin composition (A) for forming an adhesive layer (a), 2-part urethane acrylate oligomer having a benzene ring as a hard segment and an alkyl group as a repeating unit is used. A mixed liquid was prepared by mixing 50 parts of ethylhexyl acrylate and 3 parts of a photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals).
Furthermore, an ultraviolet curable acrylic hard coat agent was prepared as the UV curable resin (B) for forming the hard coat layer (b).

The release film (1) is coated with two layers of the adhesive resin composition (A) for forming the pressure-sensitive adhesive layer (a) and the UV curable resin (B) at the same time, and these two coating layers The release film (2) was laminated on the top so as not to contain bubbles. The coating layer was cured by irradiating with ultraviolet rays under the conditions of an output of 120 W / cm, a lamp distance of 150 mm, and an integrated light amount of 600 mJ / cm ² . Thereby, the adhesive film which has a layer structure of peeling film (1) / adhesive layer (a) / hard coat layer (b) / release film (2) was obtained.

  Generation | occurrence | production of VOC from the produced film was OK in order not to use an organic solvent. The ball tack of the pressure-sensitive adhesive layer (a) was 1. Further, the ball tack of the hard coat layer (c) was 0. The hard coat property was 2H in the pencil hardness test. The hard coat adhesion was OK. The cutting suitability was also OK, a clear interface could not be confirmed, and it was estimated that it was a continuous layer.

Example 4
As an example of the release films (1) and (2), a biaxially stretched polyethylene terephthalate film having a thickness of 38 μm and having a release treatment with a silicone release agent on one side was prepared.
Further, as a fluid solventless adhesive resin composition (A) for forming the adhesive layer (a), 50 parts of 2-ethylhexyl acrylate, 50 parts of 2-hydroxypropyl acrylate, 2-hydroxy-3-acrylic are used. A resin liquid consisting of 0.50 part of leuoxypropyl methacrylate and 3 parts of a photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) was prepared.
Further, as the UV curable resin (B) for forming the hard coat layer (b), a urethane acrylate oligomer having a polycarbonate skeleton as a hard segment and an alkyl group in a repeating unit and a photopolymerization initiator (trade name: Irgacure 184, A mixed liquid in which 3 parts of Ciba Specialty Chemicals) were mixed was prepared.
Furthermore, an ultraviolet curable acrylic hard coat agent was prepared as the UV curable resin (C) for forming the hard coat layer (c).

The above release film (1) is coated with the above-mentioned pressure-sensitive adhesive layer (a) adhesive resin composition (A), and the release film (2) is bonded onto the coating layer so that bubbles do not enter. It was. The resin was slightly cured by irradiating with ultraviolet rays under the conditions of an output of 120 W / cm, a lamp distance of 150 mm, and an integrated light quantity of about 50 mJ / cm ² . The release film (2) is peeled off, the release surface is coated with the UV curable resin (B) and the UV curable resin (C), and a new release film (2) is foamed on these three coating layers. It was pasted so that there was no. The coating layer was cured by irradiating with ultraviolet rays under the conditions of an output of 120 W / cm, a lamp distance of 150 mm, and an integrated light amount of 600 mJ / cm ² . Thereby, the adhesive film which has a layer structure of peeling film (1) / adhesive layer (a) / hard coat layer (b) / hard coat layer (c) / release film (2) was obtained.

  Generation | occurrence | production of VOC from the produced film was OK in order not to use an organic solvent. The ball tack of the pressure-sensitive adhesive layer (a) was 16. Further, the ball tack of the hard coat layer (c) was 0. The hard coat property was 2H in the pencil hardness test. The hard coat adhesion was OK. The cutting suitability was also OK, a clear interface could not be confirmed, and it was estimated that it was a continuous layer.

(Comparative Example 1)
As an example of the release films (1), (2), (3), (4), (5), (6), a biaxially stretched polyethylene terephthalate with a thickness of 38 μm, which has been subjected to release treatment with a silicone release agent on one side A film was prepared.
Adhesive resin composition (A) for forming an adhesive layer (a), UV curable resin (B) for forming a hard coat layer (b), UV curable resin (C) for forming a hard coat layer (c) ) Was prepared in Example 1.

The release film (1) was coated with the adhesive resin composition (A) for forming the pressure-sensitive adhesive layer (a), and then the release film (2) was bonded to prevent bubbles from entering. A laminate having a layer configuration of release film (1) / adhesive layer (a) / release film (2) by irradiating with ultraviolet rays under conditions of an output of 120 W / cm, a lamp distance of 150 mm, and an integrated light quantity of 600 mJ / cm ^2. Manufactured.
Similarly, after the release film (3) was coated with the above-described UV curable resin (B), the release film (4) was bonded to prevent bubbles from entering. A laminate having a layer structure of release film (3) / hard coat layer (b) / release film (4) by irradiating with ultraviolet rays under conditions of an output of 120 W / cm, a lamp distance of 150 mm, and an integrated light quantity of 600 mJ / cm ^2. Manufactured.
Similarly, after the release film (5) was coated with the above-described UV curable resin (C), the release film (6) was bonded to prevent bubbles from entering. A laminate having a layer structure of release film (5) / hard coat layer (c) / release film (6) by irradiating with ultraviolet rays under the conditions of an output of 120 W / cm, a lamp distance of 150 mm, and an integrated light quantity of 600 mJ / cm ^2. Manufactured.

  The release film (2) of the pressure-sensitive adhesive layer (a) and the release film (4) of the hard coat layer (b) are peeled off and bonded by a roll press, and the release film (1) / pressure-sensitive adhesive layer (a) / An adhesive film having a layer structure of hard coat layer (b) / release film (3) was obtained. Furthermore, the release film (3) of the adhesive film and the release film (6) of the hard coat layer (c) were peeled off and bonded by a roll press machine. Thereby, the adhesive film which has a layer structure of peeling film (1) / adhesive layer (a) / hard coat layer (b) / hard coat layer (c) / release film (5) was obtained.

  Generation | occurrence | production of VOC from the produced film was OK in order not to use an organic solvent. The ball tack of the pressure-sensitive adhesive layer (a) was 1. Further, the ball tack of the hard coat layer (c) was 0. The hard coat property was measured as 2H in the pencil hardness test, but there was almost no adhesion between the hard coat layer (b) and the hard coat layer (c), and it was impossible to form a laminate. It was. The cutting suitability was OK, but since a clear interface could be confirmed, it was estimated that an interface was present instead of a continuous layer.

(Comparative Example 2)
As the pressure-sensitive adhesive resin composition (A) for forming the pressure-sensitive adhesive layer (a) and the UV curable resin (C) for forming the hard coat layer (c), those prepared in Example 1 were used. A polyethylene terephthalate film (product name: E5000) manufactured by Toyobo Co., Ltd. was used for forming the hard coat layer (b).
After the adhesive resin composition (A) is coated on the hard coat layer (b) and the release film (1) is bonded so that air bubbles do not enter, the output is 120 W / cm, the lamp distance is 150 mm, and the integrated light quantity is 600 mJ / cm ^2. The coating layer was cured by irradiating with ultraviolet rays under the following conditions.
After the UV curable resin (C) is coated on the reverse side coated with the adhesive resin composition and the release film (2) is bonded to prevent bubbles from entering, the output is 120 W / cm, the lamp distance is 150 mm, and the integrated light quantity. The coating layer was cured by irradiating with ultraviolet rays at 600 mJ / cm ² .
Thereby, the adhesive film which has a layer structure of peeling film (1) / adhesive layer (a) / hard coat layer (b) / hard coat layer (c) / release film (2) was obtained.

Generation | occurrence | production of VOC from the produced film was OK in order not to use an organic solvent. The ball tack of the pressure-sensitive adhesive layer (a) was 1. Further, the ball tack of the hard coat layer (c) was 0. The hard coat property was 2H in the pencil hardness test. The hard coat adhesion was NG because peeling occurred at the film interface and a decrease in transmittance and white turbidity could be visually confirmed. The cutting suitability was OK, but since a clear interface could be confirmed, it was estimated that an interface was present instead of a continuous layer.
Furthermore, since the base film is used and there is optical anisotropy, the useable applications are limited.

(Comparative Example 3)
As an example of the release film (1), a biaxially stretched polyethylene terephthalate film having a thickness of 38 μm and having a release treatment with a silicone release agent on one side was prepared.
As the adhesive resin composition (A) for forming the adhesive layer (a), 3 parts of a polyisocyanate curing agent is added to 100 parts of 2-ethylhexyl acrylate-acrylic acid (95: 5 by weight) copolymer, Toluene solvent was added to adjust the viscosity to 500 cps. A polyethylene terephthalate film (product name: E5000) manufactured by Toyobo Co., Ltd. was used for forming the hard coat layer (b). As the UV curable resin (C) for forming the hard coat layer (c), the one prepared in Example 1 was used.

The hard coat layer (b) is coated with the pressure-sensitive adhesive layer (a) adhesive resin composition (A) and then dried at 80 ° C. so that the release film (2) does not contain bubbles. Pasted. Then, the laminated body which has a layer structure of peeling film (1) / adhesive layer (a) / hard coat layer (b) was manufactured by making it age | cure | ripen and harden | cure at 40 degreeC for one week.
Furthermore, the UV curable resin (C) was coated on the hard coat layer (b), and the release film (2) was bonded so as not to contain bubbles. The coating layer was cured by irradiating with ultraviolet rays under the conditions of an output of 120 W / cm, a lamp distance of 150 mm, and an integrated light amount of 600 mJ / cm ² . Thereby, the adhesive film which has a layer structure of peeling film (1) / adhesive layer (a) / hard coat layer (b) / hard coat layer (c) / release film (2) was obtained.

Generation | occurrence | production of VOC from the produced film was NG since the organic solvent was used. The ball tack of the pressure-sensitive adhesive layer (a) was 1. Further, the ball tack of the hard coat layer (c) was 0. The hard coat property was 2H in the pencil hardness test. The hard coat adhesion was NG because peeling occurred at the film interface and a decrease in transmittance and white turbidity could be visually confirmed. The cutting suitability was OK, but since a clear interface could be confirmed, it was estimated that an interface was present instead of a continuous layer.
Furthermore, since the base film is used and there is optical anisotropy, the useable applications are limited.

  The above evaluation results are summarized in Table 1.

  As described above, the adhesive films of Examples 1 to 4 can be confirmed by cross-sectional microscopic observation that they do not peel off at the interface of the adhesive layer (a) / hard coat layer (b) when bent by hand. When the interface of the hard coat layer (b) / adhesive layer (a) of the cross section cut with the blade is observed with a microscope, it can be confirmed that the interface has not been peeled off. A clear interface could not be observed, and it was confirmed that the layer was a continuous layer, a so-called gradient layer. From these results, the hard coat adhesion can be evaluated as “◯”. Moreover, when the adhesive film which peeled peeling film (1) and (2) was bonded to common glass, the sticking operation was also smooth. For this reason, the pasting property can be evaluated as “◯”. Therefore, the comprehensive evaluation can be evaluated as “◎”. Since the manufacturing method of the adhesive film of Examples 1-4 does not have the use of a solvent and a drying process, generation | occurrence | production of VOC can be evaluated as OK.

On the other hand, after the adhesive film of Comparative Examples 1-3 bent the adhesive film by hand, the interface of an adhesive layer (a) / hard coat layer (b) / hard coat layer (c) was cross-sectional microscope. When observing, you can confirm the part that is peeled off at the interface, when you observe the cross section of the interface with an optical microscope / polarizing microscope, you can confirm that a clear interface is observed, and that the interface is peeled off, Moreover, after peeling off a peeling film (2) gradually, when pasting to general glass, it was able to stick, but the interface of an adhesive layer (a) / hard-coat layer (b), and / or Alternatively, peeling may occur at the hard coat layer (b) / hard coat layer (c) interface, resulting in whitening. From these results, the bondability can be evaluated as “◯”, the hard coat adhesion as “×”, and the overall evaluation as “×”.
Since the manufacturing method of the adhesive film of the comparative example 3 has the drying process of a toluene solvent, generation | occurrence | production of VOC can be evaluated as NG.

  The manufacturing method of the adhesive film with a hard coat of this invention can be utilized for manufacture of various adhesive films with a hard coat, for example, an adhesive film with an optical hard coat.

It is typical sectional drawing which shows an example of the adhesive film with a hard coat of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 ... Release film (separator), 12 ... Hard coat layer, 13 ... Hard coat layer, 14 ... Adhesive layer, 15 ... Release film (separator).

Claims (8)

  On one surface of the separator having releasability, the pressure-sensitive adhesive layer has one or more ball tacks measured at an inclination angle of 30 degrees with an energy ray curing at a normal temperature according to JIS Z0237 according to JIS Z0237. Resin layer A for forming a hard coat layer in which the resin layer A for formation and the ball tack measured at an inclination angle of 30 degrees by an inclined ball tack measurement method according to JIS Z0237 at normal temperature by energy ray curing are zero After sequentially coating multiple layers, the resin layer A and the resin layer B are simultaneously cured by irradiating energy rays, thereby forming an adhesive film in which an adhesive layer is laminated on one side of the hard coat layer at a time. A method for producing a hard-coated pressure-sensitive adhesive film.   The said resin layer A and the resin layer B consist of a solventless type energy-beam curable composition, The manufacturing method of the adhesive film with a hard coat of Claim 1 characterized by the above-mentioned.   The said resin layer B consists of the resin layer which carried out the multilayer coating of at least 2 layers, and has a hard-coat property more than H by the pencil hardness test according to JISK5600-5-4,5. The manufacturing method of the adhesive film with a hard coat as described in 2.   Furthermore, the antifouling layer was laminated | stacked on the resin layer B, The manufacturing method of the adhesive film with a hard coat as described in any one of Claim 1 to 3 characterized by the above-mentioned.   Furthermore, the antireflection layer and the antifouling layer as the outermost layer were laminated on the resin layer B, The manufacturing method of the adhesive film with a hard coat as described in any one of Claim 1 to 3 characterized by the above-mentioned.   The separator is one selected from the group of flexible release bodies such as synthetic resin films, metal foils, release papers, and the like even after the resin layer A and the resin layer B are simultaneously cured. The method for producing a hard-coated pressure-sensitive adhesive film according to any one of claims 1 to 5, wherein a separator is bonded to the resin layer A.   The separator is one type selected from the group of exfoliated bodies having no flexibility such as a synthetic resin plate, a metal plate, and a glass plate, and the resin layer A and the resin layer B are simultaneously cured. The method for producing a pressure-sensitive adhesive film with a hard coat according to any one of claims 1 to 5, wherein the separator is peeled off from the resin layer A.   It is obtained by the manufacturing method as described in any one of Claims 1-7, The adhesive film with a hard coat by which the adhesive layer was laminated | stacked on the one surface of the hard-coat layer.

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