TWI545011B - Multi - layer substrate and image display device - Google Patents

Description

Multilayer substrate and image display device

The present invention relates to a multilayer substrate and an image display device including the multilayer substrate. More particularly, the present invention relates to a multilayer substrate which can be preferably used for an air gap portion or a joint portion of an image display device having a touch panel, and a touch panel image display device including the multilayer substrate.

In recent years, mobile information terminal devices equipped with flat-panel PCs and smart phones and equipped with transparent touch panels for information display and information input are widely used in Japan and the world.

From the viewpoint of miniaturization and weight reduction of the mobile information terminal device, the touch panel or the image display device mounted thereon is also required to be thinner. As a method of thinning a touch panel or an image display element, a method of reducing the number of various functional films as constituent members or a method of reducing the thickness of the functional film has been studied.

As the various functional films, in addition to films having optical or electrical properties such as antireflection, antistatic, and electrical conductivity, a protective film provided to protect the electrode (sensor) portion used in the touch panel may be used. Wait.

In order to reduce the thickness of the functional films, a substrate film which is extremely thin (for example, having a thickness of 40 μm or less) is used as a method of forming a substrate of the functional film. However, if When a functional layer is formed on a thin base film, the problem that the film is easily curled due to stress or the like generated in the forming step becomes more remarkable. The film which is curled (i.e., has low flatness) is not only difficult to handle in the manufacturing process, but also, in particular, in an image display device having a touch panel (hereinafter also referred to as "touch panel image display device"). When the sensor is used for the air gap portion or the joint portion, thickness unevenness occurs in the air gap portion or the joint portion, and thus a problem arises in that a Newton ring or the like appears due to interference of light, resulting in a touch panel. The appearance is reduced. Also, it is predicted that the sensitivity of the sensor of the touch panel will be lowered.

As a film having a functional layer and having a small amount of curling, for example, Patent Document 1 discloses a cured resin layer obtained by applying a curable composition to a substrate and curing it, and crimping after curing, etc. Less hard coating.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-147017

However, the hard coat film described in Patent Document 1 is assumed to be used for the outermost surface of the display for protecting the surface of the image display device, and is used for, for example, the air gap portion or the joint portion of the touch panel image display device. , no disclosure and tips. The base material of the hard coat film used in the examples of Patent Document 1 is a thick substrate having a thickness of 188 μm (refer to paragraph 0099), and is not suitable for use in a touch panel which is required to be thinned.

Moreover, for the functional film used for the image display device, it is required in terms of appearance. It has less color and will not yellow when stored for a long time, especially under high temperature and high humidity conditions. However, in Patent Document 1, the coloring suppression of the hard coat film is not disclosed or suggested.

On the other hand, when the base film is made thinner, the strength is lowered. Therefore, in order to improve the rationality in the production process, it is also required to maintain the flexibility of the base film and impart hardness. However, the film for protecting the sensor or the like for use in, for example, the air gap portion or the joint portion of the touch panel image display device, may have surface protection properties that can prevent damage to the sensor or the like in the manufacturing step. . Moreover, since the permanent deformation due to external stress is required to be small, and the toughness which can withstand the repeated pressing when the touch panel is operated is required, the air gap portion or the joint portion of the touch panel image display device is not suitable. Use a film with excessive rigidity.

In particular, in a mobile device including a touch panel such as a tablet PC or a smart phone, there is a case where bending or weight is applied to the display surface when it is carried in, for example, a pocket of a jacket or a trouser. Therefore, the film for a moving type touch panel image display device is required to have a degree of softness even if the force as described above is applied without breaking. Therefore, if it has only a hardness as a conventional hard coat film and does not curl, it is not sufficient as performance.

An object of the present invention is to provide a multilayer substrate and a video display device including the multilayer substrate, wherein the multilayer substrate has a protective layer on at least one surface of the base film, and the thickness of the base film is thinned. It is also produced less, has less coloration, and has less yellowing, excellent softness, and sufficient surface protection properties even under high temperature and high humidity conditions.

In particular, the present invention provides a multilayer substrate, and a touch panel image display device including the multilayer substrate, which is used for an air gap portion or a joint portion of a touch panel image display device, and has a touch Adequate surface protection properties in the manufacturing steps of the board.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies to find that a protective film is provided on at least one surface of a base film, and the thickness of the base film is 40 μm or less, and the protective layer is a curable resin having a specific composition. The cured object of the composition can solve the above problems.

That is, the present invention provides the multilayer substrate and image display device of the following [1] to [3].

[1] A multilayer substrate comprising a protective layer on at least one side of a base film, wherein the base film has a thickness of 40 μm or less, and the protective layer contains a cationic polymerizable resin and a radical polymerizable resin. A cured product of a radiation curable resin composition, and b* is 2.0 or less in a CIE1976-L*a*b* color system.

[2] A multilayer substrate comprising a protective layer on at least one side of a base film, wherein the base film has a thickness of 40 μm or less, and the protective layer contains a cationic polymerizable resin and a radical polymerizable resin. A cured product of the radiation curable resin composition, and the multilayer substrate is used for an air gap portion or a joint portion of a touch panel image display device.

[3] An image display device comprising the multilayer substrate of the above [1] or [2].

The multilayer substrate of the present invention has less curl generation, less coloration, less yellowing due to long-term storage under high temperature and high humidity conditions, excellent flexibility, and further sufficient surface protection properties. Therefore, by using, for example, a protective member inside the image display device, damage which may occur in the manufacturing process of the image display device can be prevented, and the appearance of the image display device can be prevented, and the thickness can be reduced. In particular, by using the air gap portion or the joint portion of the touch panel image display device, damage that may occur in the manufacturing steps of the touch panel image display device can be prevented, and the appearance of the touch panel can be reduced without being thinned. It's easy.

101, 102‧‧‧ touchpad image display device

10‧‧‧ Trackpad

11‧‧‧Surface protection material

12‧‧‧ Sensors

13‧‧‧Multilayer substrate

14‧‧‧ adhesive layer

20‧‧‧ Air layer forming an air gap

22‧‧‧ spacers

30‧‧‧Display components

31‧‧‧Protective materials

Fig. 1 is a cross-sectional view showing an example of a touch panel image display device having an air gap portion.

Fig. 2 is a cross-sectional view showing an example of a touch panel image display device having a joint portion.

Hereinafter, embodiments of the present invention will be described.

[Multilayer substrate]

The multilayer substrate of the present invention has a protective layer on at least one surface of the base film, and the base film has a thickness of 40 μm or less, and the protective layer contains a cationically polymerizable resin and a radically polymerizable resin. Hardened matter. The protective layer may be formed on one side of the base film or may be formed on both sides. The multilayer substrate of the present invention has curl formation even if it has a protective layer on only one side of the base film. Inhibitory effect.

In particular, the multilayer substrate of the present invention preferably has a b* of 2.0 or less in the CIE1976-L*a*b* color system.

(substrate film)

The base film used for the multilayer substrate of the present invention preferably has light transmissivity, smoothness, heat resistance and excellent mechanical strength. Examples of such a substrate film include polyester, triacetyl cellulose (TAC), cellulose diacetate, cellulose acetate butyrate, polyamine, polyimine, polyether oxime, polyfluorene, and poly. Propylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polycarbonate, polyurethane, and amorphous olefin (COP, Plastic film such as Cyclo-Olefin-Polymer (cycloolefin polymer). The base film may be formed by laminating two or more plastic films.

Among the above, a base film selected from the group consisting of a triacetyl cellulose film, a polyester film, and an acrylic film is preferable. From the viewpoint of mechanical strength or dimensional stability, polyester (polyethylene terephthalate, polyethylene naphthalate) which is subjected to elongation processing, in particular, uniaxial or biaxial stretching processing, is preferred. From the viewpoint of light transmittance and optical isotropic properties, TAC and acrylic acid are preferred.

COP and polyester are preferred in terms of ease of retardation control. Moreover, in the case of observing an image through polarized sunglasses, it is preferable to prevent a plastic film having a retardation value of 3000 to 30000 nm or a plastic film having a retardation of 1/4 wavelength in terms of unevenness in color observed on the display screen. .

The thickness of the base film is 40 μm or less from the viewpoint of reducing the thickness of the image display device, and is preferably 5 μm or more, and more preferably 15 μm or more from the viewpoint of strength.

In order to improve the adhesion, in addition to physical treatment such as corona discharge treatment or oxidation treatment, the surface of the base film may be coated with a coating called a anchoring agent or a primer.

(The protective layer)

The multilayer substrate of the present invention has a protective layer on at least one side of the substrate film from the viewpoint of enhancing the strength of the substrate film having a small thickness and the sufficient surface protection property in the manufacturing step of the image display device. . The protective layer is characterized in that, in the case of using a substrate film having a small thickness, the viewpoint of suppressing the generation of curl, and the yellowing in the case of suppressing coloring and storage under high temperature and high humidity conditions, the protective layer is characterized by: This is a cured product of a free radiation curable resin composition containing a cationically polymerizable resin and a radically polymerizable resin.

In the past, hard coating of hard coating films such as those used for the outermost surface of image display devices From the viewpoint of imparting high hardness to the layer, a curable resin composition containing a polyfunctional radical polymerizable resin as a main component is used. However, since the radically polymerizable resin has a high curing shrinkage ratio, when the radically polymerizable resin composition is applied to a base film and is irradiated with free radiation to be cured, curling due to hardening shrinkage easily occurs. . In particular, when a very thin substrate film having a thickness of 40 μm or less is used, the curl toward the resin composition side is remarkable.

On the other hand, the cationically polymerizable resin is characterized in that the curing shrinkage ratio is relatively low even if it hardens and swells and curls toward the base film side or hardens and shrinks. However, it is inferior to the radical polymerizable resin in terms of the hardness of the cured product. Further, the cured product of the resin composition containing a cationic polymerization initiator tends to be easily colored, and tends to cause yellowing particularly in the case of storage under high temperature and high humidity conditions.

However, the present inventors have found that a free radiation curable resin composition containing a cationically polymerizable resin and a radically polymerizable resin is used as a protective member for use in an image display device (for example, for a touch panel). The air gap portion or the protective member for the joint portion provided in the image display device can prevent damage which may occur in the manufacturing process of the image display device, and even when a substrate film having a thickness of 40 μm or less is used, It can also suppress the occurrence of curling, and further, it can be stored under high temperature and high humidity conditions or yellowing under external light such as sunlight, and the softness is also excellent, and the coloring is small, especially CIE1976-L*a*b * The b* in the color system is 2.0 or less.

<Free Radiation Curable Resin Composition>

The free-radiation curable resin composition used in the present invention is preferably a resin composition containing a photopolymerization initiator, various additives, and a solvent in addition to the cationically polymerizable resin and the radically polymerizable resin.

Further, the term "free radiation" means an electromagnetic wave or an energy source having a molecule capable of polymerizing or crosslinking a molecule, and generally, ultraviolet (UV) or electron beam (EB) is used, and X-rays may be used. Charged particle beams such as electromagnetic waves such as γ rays, α rays, and ion beams. In the present invention, the radically polymerizable resin and the cationically polymerizable resin are preferably ultraviolet curable resins which are cured by irradiation with ultraviolet rays.

[Cation Polymerizable Resin]

The cationically polymerizable resin which is free-radiation-curable is a compound having a cationically polymerizable functional group in the molecule and having no radical polymerizable functional group. Examples of the cationically polymerizable functional group include an epoxy group, an oxetanyl group, a vinyl ether group, an episulfide group, and an ethylenimine group, and are preferably selected from the group consisting of an epoxy group and an oxygen hetero ring. At least one of the butyl groups. In view of the strength and curability of the protective layer obtained, it is preferred to contain a compound having two or more cationically polymerizable functional groups in the molecule, and more preferably having two or more rings in the molecule. A compound of an oxy group.

The cationically polymerizable resin may have only one type of cationically polymerizable functional group, or may have two or more types.

Any of a monomer, an oligomer, and a polymer can be used for the cationically polymerizable resin used in the present invention.

Examples of the cationically polymerizable monomer used as the cationically polymerizable resin include vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, butanediol vinyl ether, and diethylene glycol divinyl ether. Phenyl epoxidized propyl ether, p-tert-butylphenyl epoxidized propyl ether, butyl epoxidized propyl ether, 2-ethylhexyl epoxidized propyl ether, allyl epoxidized ether, 1,2- Butylene oxide, 1,3-butadiene monoxide, 1,2-epoxydodecene, epichlorohydrin, 1,2-epoxydecane, benzene oxide Epoxy propyl ethers such as ethylene; 3-ethyl-3-hydroxyethyloxycyclobutane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 3 ,3-dimethyloxocyclobutane, 3,3-bis(chloromethyl)oxycyclobutane, 2-hydroxymethyloxetane, 3-methyl-3-oxocyclobutane methanol, 3 -methyl-3-methoxymethyloxycyclobutane, 3-ethyl-3-phenoxymethyloxycyclobutane, 3-ethyl-3{[(3-ethyloxycyclobutane -3-yl)methoxy]methyl}oxycyclobutane, resorcinol bis(3-methyl-3-oxetanylethyl)ether, benzyldimethyloxane, Oxy-cyclobutanes such as m-xylylene bis(3-ethyl-3-oxetanylethyl ether); epoxycyclohexane, 1,13-ditetradecadiene, dioxide Limonene, (3,4,3',4'-dihydroxy)bicyclohexane, 3,4-epoxycyclohexylmethyl (3',4'-epoxy)cyclohexanecarboxylic acid, An alicyclic epoxy compound such as bis(3,4-epoxycyclohexyl) adipate or bis(3,4-epoxycyclohexyl) sebacate.

Among the above, it is preferably selected from the group consisting of 3-ethyl-3{[(3-ethyloxycyclobutane-3-yl)methoxy]methyl}oxycyclobutane, (3, 3', 4 One or more of 4,4-dicyclooxy)bicyclohexane and 3,4-epoxycyclohexylmethyl (3',4'-epoxy)cyclohexanecarboxylic acid.

The cationically polymerizable oligomer used as the cationically polymerizable resin preferably has two or more cationically polymerizable functional groups in the molecule. Further, it is preferred that the weight average molecular weight is less than 4,000, more preferably more than 1,000 and less than 4,000. Further, the weight average molecular weight is measured by gel permeation chromatography (GPC) and determined by standard polystyrene conversion.

Examples of the oligomer include compounds represented by the following formulas (1) to (2).

In the above formula (1), a, b, and c are the average number of repetitions of the constituent units, respectively, and represent one or more. The average of a+b+c is in the range of 10~25. In the above formula (2), d is the average number of repetitions of the constituent units, and represents the number of 1 to 15.

When the cationically polymerizable oligomer is a compound represented by the above formula (1), the weight average molecular weight (weight average molecular weight in terms of polystyrene measured by a GPC method) is preferably 2,000 to 3,800. In the case where the cationically polymerizable oligomer is a compound represented by the above formula (2), the weight average molecular weight thereof is preferably from 1,200 to 2,000. Among them, the compound represented by the above formula (1) is preferred.

As a commercial item containing the compound represented by the above formula (1), "EHPE 3150" (trade name, manufactured by Daicel Co., Ltd.) or the like can be mentioned.

The weight average molecular weight (weight average molecular weight in terms of polystyrene measured by GPC method) of the polymer type cationically polymerizable resin is 4,000 in terms of suppression of curling, coloring and yellowing inhibition, and surface protection performance. The above is preferably 4,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 10,000 to 50,000.

The glass transition temperature of the polymer type cationically polymerizable resin is not particularly limited, but is preferably Higher, usually above 40 °C.

The number of functional groups of the polymer type cationically polymerizable resin is not particularly limited, and from the viewpoint of hardenability, it is preferred that the number of functional groups per molecule is large (that is, the functional group equivalent is low). The functional group equivalent of the polymer type cationically polymerizable resin is preferably 400 g/eq or less, more preferably 300 g/eq or less, still more preferably 250 g/eq or less.

Specific examples of the polymer-type cationically polymerizable resin include those having a constituent unit represented by the following formula (3).

In the formula (3), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group containing at least one cationically polymerizable functional group.

The constituent unit represented by the formula (3) is, for example, a constituent unit represented by the following (3-1) to (3-26).

In the above-mentioned constituent unit, the polymer type cationically polymerizable resin preferably has at least one constituent unit selected from the above formulas (3-1) to (3-7), and more preferably It has at least one constituent unit selected from the above formulas (3-1), (3-5), (3-6), and (3-7).

From the viewpoint of hardenability and curling, the polymer type cationically polymerizable resin is preferably contained in an amount of preferably 50 mol% or more, more preferably 75 to 100 mol%, still more preferably 90 to 100 mol%. The constituent unit represented by the above formula (3).

The polymer type cationically polymerizable resin may contain other constituent units than the constituent units represented by the above formula (3). The other constituent unit may be a constituent unit derived from a compound which can be copolymerized with a compound which can form a constituent unit represented by the above formula (3). Examples of the compound include, for example, an alkyl (meth)acrylate having an alkyl group having 1 to 12 carbon atoms, and a cycloalkyl (meth)acrylate having a cycloalkyl group having 3 to 12 carbon atoms. It is preferably a (meth) acrylate having an alkyl group having 1 to 6 carbon atoms. Further, the alkyl group, the cycloalkyl group and the like may each have a substituent.

The polymer type cationically polymerizable resin may contain only one type of the other constituent units, or may contain two or more types.

Specific examples of such a polymer type cationically polymerizable resin include 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, and 3-(methyl). a homopolymer of a compound in propylene methoxymethyl-3-ethyloxycyclobutane; a copolymer of two or more of these compounds; and other compounds which are copolymerizable with the same A copolymer of acrylate or the like.

As a commercial item of a polymer containing a glycidyl methacrylate as a structural unit, "Marproof G-01100 (weight average molecular weight: 12,000, Tg 47 ° C, epoxy equivalent: 170 g / equivalent)", "Marproof G" -0150M (weight average molecular weight 10,000, Tg 71 ° C, epoxy equivalent 310 g / equivalent)", "Marproof G-0250SP (weight average molecular weight 20,000, Tg 74 ° C, epoxy equivalent 310 g / equivalent)", etc. Made for Nippon Oil Co., Ltd.).

The above cationically polymerizable resins may be used alone or in combination of two or more.

Among the above, the cationically polymerizable resin used in the present invention is preferably a cationically polymerizable resin containing a weight average molecular weight (weight average molecular weight in terms of polystyrene measured by a GPC method) of 3,000 or more. By containing a cationically polymerizable resin having a weight average molecular weight of 3,000 or more, it is possible to obtain less curl, and it is less colored when stored under high temperature and high humidity conditions, and has excellent flexibility and is used for image display. A multilayer substrate having sufficient surface protection properties for the protective member inside the device, for example, a multilayer substrate excellent in surface protection properties in the manufacturing steps of the touch panel. Although the reason is not clear, it is presumed to be as follows.

In the cationically polymerizable resin and the radically polymerizable resin, the hardening of the radical polymerizable resin Faster. Therefore, in the curing of the free-radiation curable resin composition containing the cationically polymerizable resin and the radically polymerizable resin, first, a radical polymerization reaction is carried out to carry out crosslinking. Here, although the cationic polymerization reaction is carried out between the cationically polymerizable resins, the viscosity is increased by the progress of the radical polymerization reaction, and the progress of the cationic polymerization reaction is suppressed. Therefore, when it is predicted that only a monomer is used as the cationically polymerizable resin, the unreacted monomer remains in the cured film. The reason for the yellowing is that the unreacted monomer is detached from the cured film during storage under high temperature and high humidity conditions, or is decomposed by oxidation, hydrolysis, ultraviolet degradation, or the like.

However, the cationically polymerizable resin having a weight average molecular weight of 3,000 or more is less likely to fall off from the cured film and is less likely to be decomposed as described above. Therefore, when a cationically polymerizable resin having a weight average molecular weight of 3,000 or more is used, coloring or yellowing may occur. Fewer. Further, since the cationically polymerizable resin having a weight average molecular weight of 3,000 or more has less heat generation during curing, it is also preferable in terms of less heat damage to the base film and wrinkles on the hardened surface.

The content of the cationically polymerizable resin having a weight average molecular weight of 3,000 or more in the cationically polymerizable resin is preferably 65 mass% or more, more preferably 75 to 100 mass%, still more preferably 85 to 100 mass%. When the content is 65% by mass or more, a multilayer substrate having less curl generation, less yellowing in the case of initial coloring and storage under high temperature and high humidity conditions, and excellent surface protection properties can be obtained.

[Radical Polymerizable Resin]

In the present invention, the radically curable radical polymerizable resin refers to a compound having a radical polymerizable functional group in a molecule and having no cationic polymerizable functional group. Examples of the radical polymerizable functional group include a group containing an ethylenically unsaturated bond such as a (meth)acryl fluorenyl group, a vinyl group or an allyl group. Among them, the viewpoint of the strength and hardenability of the obtained protective layer In the case of the radically polymerizable resin, a compound having two or more ethylenically unsaturated bonds in the molecule is preferred, and more preferably two or more (meth)acryloyl groups in the molecule. A functional (meth) acrylate compound. As the polyfunctional (meth) acrylate compound, any of a monomer, an oligomer, and a polymer can be used, but from the viewpoint of strength and hardenability of the protective layer, it is preferred to contain at least a polyfunctional group. (Meth) acrylate monomer.

Among the polyfunctional (meth) acrylate compounds, examples of the bifunctional (meth) acrylate monomer include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxy diacrylate, and bisphenol. A tetrapropoxy diacrylate, 1,6-hexanediol diacrylate, and the like.

Examples of the trifunctional or higher (meth) acrylate monomer include trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, and pentaerythritol tetra (a). Base) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol tetra(meth) acrylate, iso-cyanuric acid modified tri(meth) acrylate, and the like.

Further, the (meth) acrylate monomer may be one in which a part of the molecular skeleton is modified, and ethylene oxide, propylene oxide, caprolactone, iso-cyanuric acid or an alkyl group may also be used. The cyclic alkyl group, aromatic, bisphenol, etc. are modified.

In addition, the polyfunctional (meth) acrylate oligomer is not particularly limited as long as it is a bifunctional or higher (meth) acrylate oligomer, and examples thereof include an amine ester (meth) acrylate which is low. Various (meth) acrylate oligomers such as a polymer, an epoxy (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, and a polyether (meth) acrylate oligomer Wait.

The amine ester (meth) acrylate oligomer can be obtained, for example, by the reaction of a polyol and an organic diisocyanate with a hydroxy (meth) acrylate.

Further, a preferred epoxy (meth) acrylate oligomer is a trifunctional or higher aromatic epoxy tree. a (meth) acrylate obtained by reacting a (meth)acrylic acid, such as a lipid, an alicyclic epoxy resin or an aliphatic epoxy resin, an aromatic epoxy resin having two or more functional groups, and an alicyclic epoxy resin (meth) acrylate obtained by reacting a polybasic epoxy resin with a polybasic acid or (meth)acrylic acid, and an aromatic epoxy resin having two or more functional groups, an alicyclic epoxy resin, or an aliphatic ring A (meth) acrylate obtained by reacting an oxy resin or the like with a phenol or (meth)acrylic acid.

The polyfunctional (meth) acrylate oligomer preferably has a weight average molecular weight (weight average molecular weight in terms of polystyrene measured by a GPC method) of less than 4,000, more preferably more than 1,000 and less than 3,000.

Further, the polyfunctional (meth) acrylate oligomer is more preferably a 3-12 functional group, and further preferably a 3-10 functional group. When the number of functional groups is within the above range, a protective layer excellent in strength can be obtained.

The polyfunctional (meth) acrylate polymer is not particularly limited as long as it is a bifunctional or higher (meth) acrylate polymer, and for example, an amine ester (meth) acrylate polymer or an epoxy (for example) can be used. Various (meth)acrylate polymers such as a methyl acrylate polymer, a polyester (meth) acrylate polymer, and a polyether (meth) acrylate polymer.

From the viewpoint of obtaining the above effects, the polyfunctional (meth)acrylate polymer preferably has a weight average molecular weight (weight average molecular weight in terms of polystyrene measured by a GPC method) of 4,000 or more, preferably 10,000 to 100,000, more preferably 10,000 to 50,000. When the weight average molecular weight is 100,000 or less, the curability and the coating property are good.

Further, the number of functional groups of the polyfunctional (meth) acrylate polymer is not particularly limited, and from the viewpoint of curability, it is preferred that the number of functional groups per molecule is large (that is, the functional group equivalent is low). The functional group equivalent of the polyfunctional (meth) acrylate polymer is preferably 400 g / equivalent or less, more preferably 300 g / equivalent or less, still more preferably 250 g / equivalent or less.

The above-mentioned radically polymerizable resin may be used alone or in combination of two or more.

Among them, the radical polymerizable resin used in the present invention preferably contains the above polyfunctional (meth) acrylate monomer as a main component from the viewpoint of the curability and the mechanical strength of the protective layer. The content thereof is preferably 50% by mass or more, more preferably 70 to 100% by mass, still more preferably 85 to 100% by mass based on the total amount of the radically polymerizable resin.

The radically polymerizable resin preferably contains a radically polymerizable resin having a hydroxyl group. The radically polymerizable resin having a hydroxyl group may be any of a monomer, an oligomer, and a polymer, and is preferably a monomer, more preferably the above polyfunctional (meth)acrylate monomer. By containing a radically polymerizable resin having a hydroxyl group, the strength of the obtained protective layer and the balance of curl suppression are improved. The reason for obtaining such an effect is as follows: the hydroxyl group in the radically polymerizable resin accelerates the cationic polymerization rate by a chain transfer reaction to the cationic polymerization active terminal, and is taken into the polymerization network to become a crosslinking point. The bond becomes firm and the strength of the hardened material is increased.

Further, when the radical polymerizable resin has a hydroxyl group, the water contact angle of the surface of the cured product is liable to be reduced. Therefore, it is preferable to use the multilayer substrate for the joint portion described below.

Preferred polyfunctional (meth) acrylate monomers having a hydroxyl group include pentaerythritol tri(meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol. Penta(meth)acrylate and the like. These may be used alone or in combination of two or more.

As the radical polymerizable resin, a mixture of a radical polymerizable resin having a hydroxyl group and a radical polymerizable resin having no hydroxyl group can also be used. For example, a mixture of pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol 5 ( Methyl) acrylate, and dipentaerythritol hexa(meth) acrylate a mixture of esters, etc.

In the above mixture, the ratio of the strength of the protective layer and the balance of the suppression of the curling is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 50% by mass or more. 65 mass% or more, and preferably less than 100 mass%.

The content ratio of the cationically polymerizable resin to the radically polymerizable resin in the composition of the free-radiation curable resin is preferably from 5:95 to 30:70, more preferably from 5:95 to 20:80, more preferably by mass ratio. It is 5:95~15:85. When the mass ratio of the cationically polymerizable resin is 5 or more, the occurrence of curling can be sufficiently suppressed, and a protective layer excellent in flexibility can be formed. In addition, when the mass ratio of the cationically polymerizable resin is 30 or less, it is possible to form a protective layer having less initial coloration and less yellowing when stored under high temperature and high humidity conditions, and having excellent surface protection properties.

In addition, the total content of the cationically polymerizable resin and the radically polymerizable resin in the composition of the radioactive curable resin is preferably 50% by mass or more, and more preferably 70 to 100% based on the total amount of the resin component in the composition. The mass% is further preferably 85 to 100% by mass. When the total content is 50% by mass or more, it is preferable in terms of strength and hardenability.

The free radiation curable resin composition may contain a resin component other than the cationically polymerizable resin and the radically polymerizable resin within a range that does not impair the performance of the present invention. Examples of the resin component include a thermoplastic resin, a thermosetting resin, and a compound having a cationically polymerizable functional group and a radical polymerizable functional group. When the free radiation curable resin composition contains a thermosetting resin, a curing agent may be added as needed.

From the viewpoint of hardenability, the free radiation curable resin composition preferably contains at least a photocationic polymerization initiator, more preferably a photocationic polymerization initiator and optical freedom. Base polymerization initiator. The photopolymerization initiator is not particularly limited, and those conventionally known can be used.

Examples of the photocationic polymerization initiator include an aryldiazonium salt such as p-methoxybenzenediazonium hexafluorophosphate, diphenylphosphonium hexafluorophosphate, and diphenylphosphonium hexafluoroantimonate. Iso-aryl sulfonium salt; triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]phosphonium hexafluorophosphate, diphenyl [ 4-(phenylthio)phenyl]phosphonium hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]phosphonium pentafluorohydroxy decanoate, diphenyl[4-(phenylthio) Phenyl]phosphonium tris(pentafluoroethyl)trifluorophosphate, and 4,4-bis(thenium-9-yl)-diphenyloxide di-hexafluorophosphate (compound represented by the structure below) Triaryl sulfonium salt; triphenyl selenium hexafluorophosphate, triphenyl selenium tetrafluoroborate, triphenyl selenium hexafluoroantimonate, etc.; triaryl selenium salt; dimethyl benzamidine methyl hexafluorophosphate a dialkyl benzamidine methyl phosphonium salt such as decanoate or diethyl benzamidine methyl hexafluoroantimonate; 4-hydroxyphenyl dimethyl hexafluoroantimonate, 4-hydroxyphenyl a dialkyl-4-hydroxy salt such as mercaptomethyl hexafluoroantimonate; α-hydroxymethylbenzoin isosulfonate, N-hydroxy quinone sulfonate Esters, α- one sulfonylurea group, β- ketone group Sulfonic acid esters and the like.

In addition, as a commercially available triarylsulfonium salt, "AT-6992" "AT-6976" (product name, all manufactured by ACETO); "Adeka Optomer SP-150", "Adeka Optomer" SP-170", "Adeka Optomer SP-171" (trade name, manufactured by ADEKA Co., Ltd.); "CPI-100P", "CPI-110P", "CPI-110A", "CPI-210S" (product Names, all manufactured by San-Apro (shares); "TS-91", "TS-01" (trade names, manufactured by Sanwa Chemical Co., Ltd.); "Esacure 1187", "Esacure 1188" (products) Names are manufactured by Lamberti Co., Ltd., "Omnicat 550", and "Omnicat 650" (trade names, all manufactured by IGM RESIN).

Among them, the photocationic polymerization initiator is preferably a triarylsulfonium salt, more preferably a diphenyl[4-(phenylthio)phenyl]phosphonium hexafluorophosphate, from the viewpoint of hardenability and transparency. Salt, diphenyl[4-(phenylthio)phenyl]indole tris(pentafluoroethyl)trifluorophosphate, and 4,4-bis(thenium-9-yl)-diphenyl ether di- At least one of hexafluorophosphates is further preferably diphenyl[4-(phenylthio)phenyl]phosphonium hexafluorophosphate.

These photocationic polymerization initiators may be used alone or in combination of two or more. Further, it can also be used in combination with a suitable sensitizer.

The photoradical polymerization initiator may be selected from the group consisting of acetophenone, benzophenone, α-hydroxyalkylphenone, mischrone, benzoin, benzyl methyl ketal, and benzhydryl benzoate. Acid ester, α-mercapto oxime ester, 9-oxygen sulphide One or more of the (thioxanthone) classes. Among them, α-hydroxyalkylphenone is preferred from the viewpoint of hardenability and transparency.

These photoradical polymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator in the composition of the radioactive curable resin is preferably from 1 to 20 parts by mass, more preferably from 2 to 10, per 100 parts by mass of the free radiation curable resin. Parts by mass. This content is the total amount of the photocationic polymerization initiator and the photoradical polymerization initiator.

The content ratio of the photocationic polymerization initiator to the photoradical polymerization initiator is preferably from 1:0.5 to 1:10, more preferably from 1:1 to 1:8, and still more preferably 1: 1~1:4. If When the content ratio is in the above range, sufficient strength and hardenability can be imparted, and coloring is small, and it can be suppressed from being stored under high temperature and high humidity conditions or yellowing under external light such as sunlight.

The free-radiation curable resin composition preferably contains at least one inorganic fine particle selected from the group consisting of silica and alumina, from the viewpoint of improving the strength of the protective layer and reducing the shrinkage and curing. From the viewpoint of imparting hydrophilicity to the protective layer and reducing the water contact angle of the surface of the protective layer, the cerium oxide fine particles are more preferable. The inorganic fine particles may be used singly or in combination of two or more.

Examples of the ceria fine particles include solid fine particles and hollow fine particles. However, from the viewpoint of improving the strength of the protective layer, solid fine particles are preferable. In the present invention, the term "solid microparticles" means microparticles having no voids. Since the solid fine particles are neither porous nor porous in the inside, they are not easily broken by the pressure (external pressure) applied to the particles from the outside, and are excellent in pressure resistance.

The shape of the solid cerium oxide microparticles is not particularly limited, and may be any of a substantially spherical shape, a chain shape, a needle shape, a plate shape, a sheet shape, a rod shape, and a fiber shape. In terms of improving the strength of the protective layer, it is preferably substantially spherical or chain-shaped, and more preferably ellipsoidal spheroidal cerium oxide microparticles or chain cerium oxide microparticles.

Further, in terms of improving the strength of the protective layer, the solid cerium oxide microparticles are preferably 3 to 20 spheroidal cerium oxide microparticles having an average particle diameter of 1 to 100 nm combined by inorganic chemical bonding. Alien cerium oxide microparticles.

The cerium oxide microparticles may be surface treated with a decane coupling agent, a titanate coupling agent, a fatty acid, a surfactant, or the like. For example, cerium oxide microparticles whose surface is treated with a decane coupling agent can be preferably used. The decane coupling agent can be used without particular limitation, but the hardness is imparted to the protective layer and the compatibility with the free radiation curable resin is improved to obtain transparency. The surface is preferably a decane coupling agent having at least one selected from the group consisting of a (meth)acryl fluorenyl group and an epoxy group as a functional group. The surface treatment is carried out by using the decane coupling agent, and the cerium oxide fine particles are reactive cerium oxide fine particles having at least one reactive group selected from the group consisting of a (meth) acryl fluorenyl group and an epoxy group.

As the decane coupling agent having a (meth) acrylonitrile group, for example, commercially available "KBM-502", "KBM-503", "KBE-503", and "KBM-5103" (trade name, All are manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the decane coupling agent having an epoxy group include "KBM-303", "KBM-402", "KBM-403", "KBE-402", and "KBE-403" (commercially available). Names are manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the form of the inorganic fine particles include a solid form or a colloidal form dispersed in a solvent. However, those dispersed in a solvent are excellent in terms of dispersibility in the protective layer. The average primary particle diameter of the inorganic fine particles is usually from about 1 to 300 nm, preferably from 1 to 150 nm, and more preferably from 5 to 75 nm in terms of transparency of the protective layer.

In the present invention, when the particles are in the form of primary particles which are not in the form of aggregated particles, the average primary particle diameter of the particles can be calculated by the following operations (1) to (3). .

(1) A surface image of a scanning transmission electron microscope (TEM, STEM) is imaged by applying a dispersion of the particles themselves or a dispersion of the particles to a transparent substrate (observation conditions: an accelerating voltage of 10 to 30 kV, The observation magnification is 50,000 times to 300,000 times).

(2) Any 10 particles were selected from the surface image, and the major axis and the minor axis of each particle were measured, and the particle diameter of each particle was calculated from the average of the long diameter and the short diameter.

(3) Perform the same operation 5 times in the shooting of different pictures of the same sample, which will be totaled The number of the particle diameters of the 50 primary particles is averaged to obtain an average primary particle diameter.

Further, when the particles are in the form of agglomerated particles, the particle diameter of each of the aggregated particles can be calculated from the average of the major axis and the minor axis of the aggregated particles, and the average particle size can be calculated. Specifically, any two condensed particles are selected from the surface image or the cross-sectional image of the multilayer substrate which is imaged by a scanning transmission electron microscope (TEM, STEM) (in the case of a surface image, two randomly selected, However, in the case of a cross-sectional image, since it is not clear where the particles are cut, two particles as large as possible are selected, and the long diameter and the short diameter of each aggregated particle are measured, and the particle diameter of each aggregated particle is calculated. The same operation was performed 9 times in the shooting of different images of the sample, and the average particle diameter of the aggregated particles was averaged from the total number of the aggregated particles of 20 aggregated particles (observation condition: acceleration voltage 10 to 30 kV, observation) The magnification is 50,000 times to 300,000 times). Furthermore, the long diameter system is the longest path on the screen of agglomerated particles. Further, the short diameter refers to a line segment which is orthogonal to a point in a line segment constituting the long diameter, and a distance between the orthogonal line segment and the two points at which the agglomerated particles intersect.

The content of the inorganic fine particles in the composition of the free-radiation-curable resin is preferably from 10 to 70% by mass, and more preferably from 15 to 60% by mass, based on the total amount of the radical radiation-curable resin and the inorganic fine particles. When the content of the inorganic fine particles is 10% by mass or more, the effect of improving the strength of the protective layer and the effect of suppressing the occurrence of curl by the reduction of the hardening shrinkage can be obtained. In addition, when it is 70% by mass or less, the curability or film formability is not impaired.

Further, the free radiation curable resin composition may further contain an additive such as a photopolymerization accelerator, a refractive index adjuster, an antiglare agent, an antifouling agent, an antistatic agent, a leveling agent, and a slip agent.

The photopolymerization accelerator can reduce the polymerization inhibition by air due to curing and improve the curability, and examples thereof include, for example, p-amylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, and the like. One or more of them.

The antistatic agent is not particularly limited, and examples thereof include a cationic antistatic agent such as a quaternary ammonium salt or a pyridinium salt; and an anionic property such as a sulfonate, a sulfate salt, a phosphate salt or a phosphonate. Antistatic agent; alkyl betaine and its derivatives, imidazoline and its derivatives, amphoteric antistatic agents such as alanine and its derivatives; amino alcohol and its derivatives, glycerin and its derivatives, polyethylene A nonionic antistatic agent such as a diol or a derivative thereof; an organometallic compound such as an alkoxide of tin and titanium; a metal chelate compound such as an acetoacetate of the organometallic compound. An ion conductive polymer obtained by polymerizing or copolymerizing a monomer having various cationic, anionic or zwitterionic ionic conductive groups may also be used.

As the antistatic agent, at least one selected from the group consisting of an alkali metal salt and an ionic liquid can be preferably used. Examples of the alkali metal salt include alkali metal ions such as Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , and Cs ⁺ , and halogen ions such as Cl ^- , Br ^- and I ^- , SO ₄ ^2- , NO ₃ ^- , and ClO. _a salt obtained by combining an anion such as ₄ ^- , BF ₄ ^- , PF ₆ ^- , various sulfonate ions or COO ^- or an anion such as a perchlorate ion. Among the alkali metal salts, a lithium salt is preferred.

The ionic liquid refers to a molten salt which is liquid at room temperature (25 ° C). Examples of the ionic liquid include a cationic substance such as an imidazolium group, a pyridinium system, a quaternary ammonium system, or a quaternary phosphonium system, and a halogen ion such as Cl ⁻ , Br ⁻ or I ⁻ as a counter ion, and SO ₄ ^{2 . - a} salt (liquid) in which an anion such as NO ₃ ^- , ClO ₄ ^- , BF ₄ ^- , PF ₆ ^- , various sulfonate ions or COO ^- or an anion such as a perchlorate ion is combined.

Further, as the antistatic agent, a conductive polymer such as polyaniline, polyacetylene, polypyrrole, polythiophene or polyvinylcarbazole; a carbonaceous material such as fullerene or a carbon nanotube; indium oxide or zinc oxide; , tin oxide, potassium titanate, titanium oxide, tin-bismuth oxide, indium-tin oxide, A metal oxide material such as bismuth-tin oxide.

The antistatic agents may be used alone or in combination of two or more. Among the antistatic agents, a cationic antistatic agent such as a quaternary ammonium salt or a pyridinium salt or a polymer thereof is preferably used in terms of an antistatic effect and compatibility with the free radiation curable resin. At least one of the alkali metal salts is more preferably at least one selected from the group consisting of a quaternary ammonium salt or a polymer thereof and a lithium salt.

The content of the antistatic agent in the composition of the radioactive curable resin can be appropriately selected according to the sensor sensitivity of the touch panel, etc., and is not particularly limited, and is preferably 100 parts by mass based on the free radiation curable resin. It is 1 to 15 parts by mass, more preferably 2 to 10 parts by mass, still more preferably 3 to 8 parts by mass. When the content is 1 part by mass or more, sufficient antistatic property can be imparted. Moreover, when it is 15 mass parts or less, precipitation or bleed-out of an antistatic agent can be avoided.

Further, the free radiation curable resin composition may contain a solvent. The solvent is not particularly limited as long as it is a solvent for dissolving each component contained in the resin composition, and is preferably a ketone or an ester, more preferably selected from methyl ethyl ketone and methyl group. At least one of isobutyl ketones. These solvents may be used alone or in combination of two or more.

The content of the solvent in the composition of the radiation-hardening resin is usually 20 to 90% by mass, preferably 30 to 85% by mass, more preferably 40 to 80% by mass. When the content of the solvent is within the above range, the coating suitability is excellent.

The protective layer can be formed by applying a free radiation curable resin composition onto the base film to form a coating layer, and then drying it as necessary after the drying step.

The coating layer can be prepared by coating a free radiation curable resin composition prepared by mixing other components such as a cationically polymerizable resin, a radically polymerizable resin, and a photopolymerization initiator. And formed.

Further, it is also possible to form a resin composition containing a cationically polymerizable resin and a resin composition containing a radical polymerizable resin, and sequentially apply them to a base film. In this case, the order of application is not particularly limited, and from the viewpoint of imparting strength to the surface of the protective layer and causing less curling, it is more preferable to apply the resin composition containing the cationically polymerizable resin. The cloth contains a resin composition of a radical polymerizable resin. Further, in terms of the adhesion between the layers, a coating layer of a resin composition containing a cationically polymerizable resin is formed, and then a coating layer of a resin composition containing a radical polymerizable resin is formed. After the irradiation of the free radiation, the respective coating layers are simultaneously hardened.

The method of applying the composition of the free-radiation curable resin may be a method which can be uniformly applied to a desired thickness, and may be appropriately selected from conventionally known methods. For example, a gravure coating method, a doctor blade method, a dip coating method, a spray coating method, an air knife coating method, a spin coating method, a roll coating method, a curtain coating method, a die coating method, and a flow may be mentioned. Extension method, stick coating method, extrusion coating method.

Then, after the drying step is performed as needed, the coating layer is irradiated with free radiation such as an electron beam or an ultraviolet ray to cure the coating layer. In the case where an electron beam is used as the radical radiation, the acceleration voltage can be appropriately selected depending on the thickness of the resin or layer to be used, and it is usually preferred to cure the coating layer at an acceleration voltage of about 70 to 300 kV.

When ultraviolet rays are used as the free radiation, ultraviolet rays containing a wavelength of 190 to 380 nm are usually emitted. The ultraviolet light source is not particularly limited, and for example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp or the like can be used. The ultraviolet irradiation is preferably carried out under a nitrogen atmosphere having an oxygen concentration of 1000 ppm or less.

The ultraviolet ray irradiation can be carried out at one time, or in order to prevent wrinkles on the surface of the cured product due to heat generation upon irradiation with ultraviolet rays, the ultraviolet ray irradiation is performed in multiple steps.

The thickness of the protective layer (at the time of curing) can be appropriately selected depending on the thickness of the base film, etc., but it is preferably 2 μm or more and less than 20 μm, more preferably 2, in terms of imparting sufficient strength and suppressing generation of curl. It is preferably 15 to 15 μm, more preferably 3 to 12 μm. When the thickness of the protective layer is 2 μm or more, surface protection performance and flexibility are good, and if it is less than 20 μm, flexibility can be maintained and curl generation can be suppressed.

The thickness of the protective layer can be measured, for example, from the image of the cross-section imaged by a transmission electron microscope (TEM), and is calculated from the average of the values at 20.

Further, in terms of imparting sufficient strength and suppressing generation of curl, the thickness ratio of the protective layer to the base film (the thickness of the protective layer / the thickness of the base film) is preferably 0.04 to 5, more preferably 0.05. 2, further preferably in the range of 0.05 to 0.5.

(other layers)

The multilayer substrate of the present invention may further have other functional layers such as an antireflection layer, an antistatic layer, a refractive index adjusting layer, and an antifouling layer on either side of the substrate film. Among them, the multilayer substrate preferably has an antireflection layer from the viewpoint of reducing reflection on the surface of the display. In this case, the multilayer substrate has a base film, a protective layer, and an antireflection layer in this order, and preferably has an antireflection layer on the outermost surface of the multilayer substrate.

The antireflection layer may be a single layer structure composed of a layer having a lower refractive index than the protective layer. Further, it may be a multilayer structure in which a high refractive index layer and a low refractive index layer are sequentially provided from the side of the protective layer, and the outermost surface layer is a low refractive index layer, and the thickness d of each layer satisfies d=m λ/4n. Here, m denotes a positive odd number, n denotes a refractive index of a low refractive index layer, and λ denotes a wavelength. m is preferably 1. λ Preferably, it is 450 to 700 nm, more preferably 500 to 600 nm.

The low refractive index layer and the high refractive index layer can also be formed by a method such as vacuum vapor deposition or sputtering using, for example, low refractive index fine particles or high refractive index fine particles. Examples of the low refractive index fine particles include SiO ₂ (refractive index n=1.45), MgF ₂ (refractive index n=1.38), LiF (refractive index n=1.36), NaF (refractive index n=1.33), and CaF _{2 .} Fine particles of a metal oxide such as (refractive index n=1.44), 3NaF-AlF ₃ (refractive index n=1.4), AlF ₃ (refractive index n=1.37), Na ₃ AlF ₆ (refractive index n=1.33), and the above Hollow particles, etc. Further, examples of the high refractive index fine particles include Al ₂ O ₃ (refractive index n=1.63), La ₂ O ₃ (refractive index n=1.95), ZrO ₂ (refractive index n=2.05), and Y ₂ O ₃ (refraction). The rate of n = 1.87) is a fine particle of a metal oxide.

In view of the fact that it is easier to form a layer, it is preferable to form the fine particles by a known method using, for example, a resin composition dispersed in the free radiation curable resin used in the protective layer. Further, for example, a low refractive index layer may preferably contain two fluorine-containing compounds such as the above-mentioned low refractive index fine particles, a vinylidene fluoride copolymer or a polyfluorene-containing vinylidene fluoride copolymer, and have two in one molecule. The above reactive functional group is formed, for example, as a fluorinated monomer having a pentaerythritol skeleton or a curable resin composition such as a free radiation curable resin.

Further, the multilayer substrate of the present invention may have a structure having an antistatic layer. The antistatic layer is preferably disposed at a position in contact with at least one side of the protective layer. For example, the substrate film, the antistatic layer, and the protective layer are sequentially provided; the substrate film, the protective layer, and the antistatic layer are sequentially provided; the substrate film, the antistatic layer, and the protective layer are sequentially provided; The composition of the layer and the antistatic layer.

The antistatic layer may, for example, be a layer formed using a resin composition containing the above antistatic agent. The resin to be contained in the resin composition is not particularly limited as long as it is a transparent resin which can contain the above antistatic agent, and examples thereof include a thermoplastic resin and thermosetting. Resin, free radiation curable resin, and the like.

The method of forming the antistatic layer is not particularly limited, and a usual coating method can be used. The thickness of the antistatic layer is not particularly limited as long as it can provide a desired antistatic property.

When used in an image display device, such as an air gap portion or a joint portion of a touch panel image display device, it exhibits sufficient surface protection performance in the manufacturing steps thereof, and the image display device is thinned. The total thickness of the multilayer substrate of the present invention is preferably from 23 to 70 μm, more preferably from 25 to 50 μm.

(Characteristics of multilayer substrates)

The multilayer substrate of the present invention is characterized in that it is less colored and has less yellowing even under long-term storage under high temperature and high humidity conditions. Regarding the coloring of the multilayer substrate, specifically, in the CIE1976-L*a*b* color system, b* is preferably 2.0 or less, more preferably 1.0 or less, still more preferably 0.50 or less. When the b* of the multilayer substrate is 2.0 or less, the appearance is good when used for an image display device such as a touch panel image display device.

Further, regarding the yellowing under high temperature and high humidity conditions, when the multilayer substrate of the present invention is stored at a temperature of 80 ° C and 90% RH for 500 hours, the Δb* before and after storage is preferably less than 0.70, more preferably It is 0.40 or less, and further preferably 0.20 or less.

Specifically, the value of b* can be measured by the method described in the examples.

The multilayer substrate of the present invention is characterized by less curl generation. The degree of curling is preferably from 60 to 100 mm, more preferably from 30 to 100 mm, when the multilayer substrate of the present invention is cut into 100 mm × 100 mm and placed at a horizontal plane. The term "the shortest distance between the ends of the multilayer substrate" means the shortest distance between the opposite sides of the multilayer substrate which is curled, and the shortest distance between the diagonals of the multilayer substrate which is curled, Or the shortest distance of the shortest distance between one of the sides of the laminated multilayer substrate and the corner opposite the side. The shortest distance is 100 mm when no curl is generated, and the shortest distance is 0 mm when the curl is cylindrical. Specifically, the evaluation of the curl can be carried out by the method described in the examples.

Moreover, in the case of use in an air gap portion or a joint portion of an image display device such as a touch panel image display device, the multilayer base of the present invention is obtained from the viewpoint of exhibiting sufficient surface protection performance in the manufacturing step thereof. The pencil hardness of the surface of the protective layer of the material is preferably H or more, more preferably 2H or more, and still more preferably 3H or more. In particular, in the case of being used for the air gap portion, the pencil hardness is preferably H or more from the viewpoint of preventing deformation from the external force application. Further, in the case of use in the joint portion, in order to bring the multilayer substrate into contact with the bonding layer described below, the pencil hardness of the surface of the protective layer is preferably 2H or more. The pencil hardness can be evaluated in accordance with JIS K5600-5-4, and specifically, it can be measured by the method described in the examples.

The multilayer substrate of the present invention can be preferably used in an image display device. In particular, it can be used for a protective member inside the image display device, for example, for the purpose of mainly preventing damage of the sensor portion in the touch panel manufacturing step, and for being used in the air gap portion or the joint portion of the touch panel image display device.

Here, the water contact angle of the outermost surface of the multilayer substrate of the present invention is not particularly limited. When used for the joint portion of the touch panel image display device, the temperature of the outermost surface of the multilayer substrate is 25 ° C. The water contact angle at a humidity of 50% is preferably 80 or less, more preferably 70 or less. When the water contact angle is 80 or less, the adhesion to the bonding layer of the touch panel image display device is good, and even when it is bonded to the bonding layer, bubbles are hard to enter. Further, the water contact angle is preferably 40 or more in terms of easy peeling of the bonding layer or the like when the product is defective.

Moreover, in the same viewpoint as described above, the multilayer substrate of the present invention is used for a touch panel shadow In the case of a joint portion of a display device, the contact angle of the outermost surface of the multilayer substrate at a temperature of 25 ° C and a humidity of 50% is preferably 25 or less, more preferably 20 or less, and is preferably. It is 2° or more.

The contact angle can be measured in accordance with JIS R3257 (1999) "Test method for wettability of substrate glass surface".

When the multilayer substrate of the present invention is used for the air gap portion, the surface reflectance is preferably 1.1% or less. This is because when the surface reflectance of the multilayer substrate is high, there is a decrease in brightness due to the reflection or a decrease in visibility due to the generation of the Newton's ring. From this point of view, the surface reflectance of the multilayer substrate is more preferably 0.5% or less, still more preferably 0.35% or less. The surface reflectance is obtained, for example, by bonding the surface of the base film side of the multilayer substrate to a black acrylic plate via an adhesive, and measuring the positive reflectance of 5° by a spectroscope.

As a method of reducing the surface reflectance of the multilayer substrate, a method of providing the antireflection layer on the outermost surface, and the like can be mentioned.

[Image display device]

The image display device of the present invention comprises the multilayer substrate of the present invention. The image display device is not particularly limited, and examples thereof include a liquid crystal display device (LCD), a plasma display device (PDP), an inorganic and organic EL display device, an electronic paper display, and a touch panel image display device. From the viewpoint of satisfying the requirements for thinning and the various effects imparted by the multilayer substrate of the present invention, a touch panel image display device is preferred. For example, since the air gap portion or the joint portion of the touch panel image display device is provided with the multilayer substrate of the present invention, uneven thickness of the air gap portion or the joint portion due to low flatness of the multilayer substrate can be avoided. The resulting appearance is reduced, the sensitivity of the sensor is reduced, and the like. As the touch panel, a capacitive touch panel, a resistive touch panel, an optical touch panel, an ultrasonic touch panel, and an electromagnetic induction touch panel can be cited. Touchpad image display The device can be either an on-cell type or an in-cell type.

Here, the air gap portion of the touch panel image display device refers to a portion where the spacer is provided between the touch panel and the display element at a gap (air gap) of about 0.5 to 1 mm. By having this air gap, there is a structure that does not affect the display element even when the surface protective material such as glass provided on the outermost surface of the touch panel is broken by an external impact.

Fig. 1 is a cross-sectional view showing an example of a touch panel image display device having an air gap portion. In Fig. 1, a 10-series touch panel, 20 is an air layer forming an air gap, 22 is a spacer, and 30 is a display element.

The touch panel 10 has a surface protective material 11, a sensor 12, and a multilayer substrate 13 in this order. The multilayer substrate 13 has at least a base film and a protective layer as described above. Further, from the viewpoint of protecting the sensor, the multilayer substrate 13 is preferably provided so that the surface on the side of the protective layer faces the air gap side.

In the touch panel image display device having the configuration of FIG. 1, the multilayer substrate 13 is preferably sequentially provided from the viewpoint of reducing interface reflection caused by the difference in refractive index between the touch panel 10 and the air layer 20. The structure of the base film, the protective layer, and the antireflection layer. In this case, the multilayer substrate 13 is preferably provided such that the surface on the side of the antireflection layer faces the air gap side.

As the surface protective material 11, a glass or a plastic substrate or the like can be used.

In FIG. 1, the sensor 12 is bonded to the surface protection material 11 via the adhesive layer 14, but in the touch panel image display device of the present invention, the sensor 12 may be directly formed on the surface protection material 11.

The display element 30 may also have a protective material 31 on the side of the air gap side. As the protective material 31, the multilayer substrate of the present invention can also be used. The multilayer substrate is also preferably provided such that the surface on the side of the protective layer faces the air gap side. Moreover, the interface caused by the difference in refractive index between the air layer 20 and the display element 30 is reduced. From the viewpoint of reflection, the multilayer substrate preferably has a base film, a protective layer, and an antireflection layer in this order, and is preferably provided such that the surface on the side of the antireflection layer faces the air gap side.

On the other hand, in the touch panel image display device 101 of the configuration shown in FIG. 1, as described above, the display element 30 (or the protective material 31), the air layer 20, and the touch panel 10 have refractive indices different from each other, There is a situation in which each interface (the interface between the display element and the air layer, the interface between the air layer and the touch panel, and the interface between the touch panel and the external atmosphere) respectively generates light reflection, thereby causing a decrease in brightness or the like.

Therefore, a touch panel image display device in which the air layer 20 is sealed with a transparent resin (joining layer) having a refractive index close to that of the touch panel 10 is also proposed. In the present specification, a portion of the touch panel image display device that is in contact with the bonding layer is referred to as a bonding portion.

Fig. 2 is a cross-sectional view showing an example of a touch panel image display device having a joint portion.

In the touch panel image display device 102 of FIG. 2, a 10-series touch panel, a 24-series bonding layer, and a 30-series display element. Since the bonding layer 24 has a refractive index close to that of the touch panel 10, by this configuration, light reflection at each interface between the respective layers in the touch panel image display device 101 of FIG. 1 can be reduced.

In the touch panel image display device 102, the touch panel 10 is also configured in the same manner as in the case of FIG. 1, and has a surface protective member 11, a sensor 12, and a multilayer substrate 13 in this order. However, since the refractive index of the bonding layer 24 is close to the touch panel 10, an anti-reflection layer is not required in the multilayer substrate 13. Further, the display element 30 may have a protective material (not shown) on the side of the bonding layer side.

The resin used for the bonding layer 24 is not particularly limited as long as it has a refractive index close to the touch panel 10 and is less colored and has high transparency. Weatherability, From the viewpoint of mechanical strength, visibility (with or without Newton's ring), as the bonding layer 24, it is preferable to use a transparent optical adhesion (OCA) film or a hardenability which can be hardened by irradiation with heat or free radiation. A cured product of a resin composition or the like.

As the composition of the free-radiation-curable resin, the same as the resin composition described in the formation of the protective layer, any of a cationically polymerizable resin and a radically polymerizable resin can be used.

Examples of the display element 30 include a liquid crystal display element, an in-line touch panel liquid crystal display element, an EL display element, a plasma display element, and the like.

The built-in touch panel liquid crystal element is incorporated in a liquid crystal element in which a liquid crystal is sandwiched between two glass substrates, and a touch panel function such as a resistive film type, a capacitive type, or an optical type is incorporated. Further, examples of the display method of the liquid crystal in which the touch panel liquid crystal element is embedded include an IPS method, a VA method, a multi-domain method, an OCB method, an STN method, and a TSTN method. The embedded touch panel liquid crystal element is described, for example, in JP-A-2011-76602 and JP-A-2011-222009.

[Examples]

The invention will now be described in more detail by way of examples, but the invention is not limited by the examples. In addition, unless otherwise indicated, "part" and "%" are set as the quality standard.

(Synthesis Example 1) Synthesis of a homopolymer of 3,4-epoxycyclohexylmethyl methacrylate

Adding 4 parts of 3,4-epoxycyclohexylmethyl methacrylate, 50 parts of methyl isobutyl ketone (MIBK), and azobis to a four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser, and a thermometer. 0.48 parts of butyronitrile (AIBN) and 0.49 parts of dodecyl mercaptan were heated to 85 ° C while stirring under a nitrogen atmosphere for 3 hours. The solid content of the obtained polymer solution was 50%, and analysis by GPC revealed that the weight average molecular weight (in terms of polystyrene) of the polymer was 15,000.

(Synthesis Example 2) Synthesis of 3,4-epoxycyclohexylmethyl methacrylate/methyl methacrylate/n-butyl methacrylate copolymer

43.2 parts of 3,4-epoxycyclohexylmethyl methacrylate, 2.4 parts of methyl methacrylate and 2.4 parts of n-butyl methacrylate were added to a four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer. 50 parts of MIBK, 0.48 parts of AIBN, and 0.25 parts of dodecyl mercaptan were heated to 85 ° C while stirring under a nitrogen atmosphere for 3 hours. The solid content of the obtained polymer solution was 50%, and analysis by GPC revealed that the weight average molecular weight (in terms of polystyrene) of the polymer was 26,000.

(evaluation method) (1) Determination of the thickness of the protective layer

The thickness of the protective layer in the multilayer substrate obtained in the examples and the comparative examples was measured at a thickness of 20 points from the image of the cross section taken by a transmission electron microscope (TEM), and was calculated from the average value of the values at 20.

(2) Curl evaluation

The multilayer substrate obtained in the examples and the comparative examples was cut into 100 mm × 100 mm and placed on a horizontal plane. Measuring the shortest distance between the ends of the multilayer substrate by the ruler (the shortest distance from the opposite sides of the multilayer substrate, the shortest distance between the diagonals of the multilayer substrate, or one side of the multilayer substrate and the side) The shortest distance from the shortest distance to the corner), and based on the following criteria Evaluation.

A; 30~100mm

B; more than 0mm and less than 30mm

C; 0mm (cylindrical)

(3) Coloring evaluation (initial coloring b*)

The initial coloring of the multilayer substrate obtained in the examples and the comparative examples was carried out by using a spectroscope ("UVPC 2450" manufactured by Shimadzu Corporation) and measuring b* at five places by a penetration method, and calculating from the average value.

(△b* when stored under high temperature and high humidity conditions)

After the initial coloring (b*) of the multilayer substrate was measured, the multilayer substrate was stored under the conditions of a temperature of 80 ° C and 90% RH for 500 hours, and b* was measured by the same method as above to obtain a preservation. △ b* before and after. The smaller the value of b* after storage, and the smaller the Δb*, the better the result.

(4) Pencil hardness

With respect to the multilayer substrate obtained in the examples and the comparative examples, the pencil hardness of the surface of the protective layer was measured by a method according to JIS K5600-5-4 (1999) at a load of 500 g.

(5) Softness evaluation (mandrel test)

For the multilayer substrate obtained in the examples and the comparative examples, the mandrel test was carried out in accordance with the cylindrical mandrel method prescribed in JIS K5600-5-1. The values listed in Table 1 (mm When the protective layer is set to the outside and is wound around the mandrel bar, the minimum mandrel diameter of the peeling or cracking of the protective layer is not generated. The smaller the value, the more excellent the flexibility.

Example 1

The composition of the free-radiation curable resin of the composition shown in Table 1 was applied to a substrate film (triacetyl cellulose (TAC) film, "thickness: 25 μm, manufactured by Konica Minolta Co., Ltd.), and dried at 70 ° C. Then, the free radiation curable resin composition was cured by irradiating ultraviolet rays so as to have an integrated light amount of 250 mJ/cm ^{2 to} form a protective layer, and the thickness of the protective layer was 7 μm.

The above evaluation was carried out on the obtained multilayer substrate. The evaluation results are shown in Table 1.

Examples 2 to 16 and Comparative Examples 1 to 3

A multilayer substrate was obtained in the same manner as in Example 1 except that the composition of the base film, the thickness of the protective layer, and the composition of the free radiation curable resin composition for forming a protective layer was changed as shown in Table 1. The evaluation results are shown in Table 1.

The ingredients shown in Table 1 are as follows. Further, the parts by mass in the table indicate the parts by mass of the solid content excluding the solvent.

<Cation Polymerizable Resin>

‧ polymer 1; a homopolymer solution of 3,4-epoxycyclohexylmethyl methacrylate synthesized in Synthesis Example 1 (50% by mass of MIBK solution, Mw 15,000)

‧ polymer 2; 3,4-epoxycyclohexylmethyl methacrylate/methyl methacrylate/n-butyl methacrylate (mass ratio 90/5/5) copolymer solution synthesized in Synthesis Example 2 ( 50% by mass of MIBK solution, Mw26,000)

‧ polymer 3; polymer containing glycidyl methacrylate unit (Marproof G-01100, manufactured by Nippon Oil Co., Ltd., Mw 12,000, epoxy equivalent 170 g/eq)

‧ oligomer; a cationically polymerizable polyfunctional oligomer represented by the above formula (1) ("EHPE 3150" manufactured by Daicel Co., Ltd., Mw 3, 200, epoxy equivalent: 179 g / equivalent)

‧ a cationically polymerizable monomer; a bifunctional cationically polymerizable monomer represented by the following structural formula ((3,4,3',4'-diepoxy)bicyclohexane)

<Free radical polymerizable resin>

‧Free radical polymerizable monomer 1; a mixture of neopentyl alcohol triacrylate and neopentyl alcohol tetraacrylate ("KAYARAD PET-30" manufactured by Nippon Kayaku Co., Ltd.)

‧Free radical polymerizable monomer 2; dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylic acid Mixture of esters ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.)

‧Free radical polymerizable monomer 3; a mixture of neopentyl alcohol triacrylate and neopentyl alcohol tetraacrylate (ARONIX M-306) manufactured by East Asia Synthetic Co., Ltd., content of pentaerythritol triacrylate ;65~70% by mass)

‧Free radical polymerizable monomer 4; a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (ARONIX M-403) manufactured by East Asia Synthetic Co., Ltd., dipentaerythritol pentaacrylic acid Ester content; 50~60% by mass)

‧Free radical polymerizable oligomer; polyfunctional amine ester acrylate oligomer ("UV-1700B" manufactured by Synthetic Chemical Industry Co., Ltd., Mw2,000, functional group number 10)

‧Free radical polymerizable polymer; Polyfunctional polymer acrylate (Beamset 371, manufactured by Arakawa Chemical Industries Co., Ltd., Mw 40,000, acrylic equivalent 400 g / equivalent)

<Photocationic polymerization initiator>

‧CPI-100P; a 50% by mass propylene carbonate solution of a triarylsulfonium salt photocationic polymerization initiator (diphenyl[4-(phenylthio)phenyl)phosphonium hexafluorophosphate having the following structure, San -Apro (share) manufacturing)

<Photoradical polymerization initiator>

‧Irgacure 184; 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF)

<additive>

‧Leveling agent; Fluorine leveling agent ("F477" made by DIC)

‧Antistatic agent; quaternary ammonium salt type antistatic polymer ("1SX-1055F" manufactured by Taisei Fine Chemical Co., Ltd.)

‧ cerium oxide microparticles; "MIBK-SD" manufactured by Nissan Chemical Industry Co., Ltd., cerium oxide dispersion, solvent MIBK, cerium oxide 30%, average primary particle size 12 nm

<solvent>

‧MIBK; methyl isobutyl ketone

‧MEK; methyl ethyl ketone

As is apparent from the results of Table 1, the multilayer substrate of the present embodiment has less curling, initial coloration, and yellowing due to high-temperature and high-humidity storage, high pencil hardness, and sufficient surface protection properties. On the other hand, in the multilayer substrate of Comparative Example 1, since the curable resin composition forming the protective layer does not contain the cationically polymerizable resin, the curling is remarkable, and the multilayer substrate of Comparative Example 2 is further inferior in flexibility. In the multilayer substrate of Comparative Example 3, since the curable resin composition forming the protective layer does not contain a radical polymerizable resin, yellowing occurs when stored under high temperature and high humidity conditions, and the hardness of the surface of the protective layer is higher. Low, so the surface protection performance is also low.

[Industrial availability]

The multilayer substrate of the present invention has less curl generation, less coloration, less yellowing due to long-term storage under high temperature and high humidity conditions, excellent flexibility, and thus sufficient surface protection properties, especially It has sufficient surface protection properties in the manufacturing steps of the touch panel. Therefore, by way of example, as a protective member inside the image display device, more specifically The air gap portion or the joint portion of the touch panel image display device can prevent damage that may occur in the manufacturing steps of the image display device such as a touch panel, and can be reduced in thickness without impairing the appearance of the image display device. It's easy.

10‧‧‧ Trackpad

11‧‧‧Surface protection material

12‧‧‧ Sensors

13‧‧‧Multilayer substrate

14‧‧‧ adhesive layer

20‧‧‧ Air layer forming an air gap

22‧‧‧ spacers

30‧‧‧Display components

31‧‧‧Protective materials

101‧‧‧Touchpad image display device

Claims (13)

A multilayer substrate comprising a protective layer on at least one surface of a base film, wherein the base film has a thickness of 40 μm or less, and the protective layer contains free radiation curability of a cationically polymerizable resin and a radical polymerizable resin. A cured product of a resin composition, and b* is 2.0 or less in a CIE1976-L*a*b* color system; the multilayer substrate further has an antireflection layer. A multilayer substrate comprising a protective layer on at least one surface of a base film, wherein the base film has a thickness of 40 μm or less, and the protective layer contains free radiation curability of a cationically polymerizable resin and a radical polymerizable resin. A cured product of a resin composition, and the multilayer substrate is used for an air gap portion or a joint portion of a touch panel image display device. The multilayer substrate according to claim 1 or 2, wherein the cationically polymerizable resin contains a cationically polymerizable resin having a weight average molecular weight of 3,000 or more. The multilayer substrate according to the first or second aspect of the invention, wherein the content ratio of the cationically polymerizable resin to the radical polymerizable resin in the free-radiation curable resin composition is 5:95 by mass ratio. 30:70. The multilayer substrate of claim 1 or 2, wherein the free radiation curable resin composition contains a photocationic polymerization initiator and a photoradical polymerization initiator, and the content ratio thereof is 1 by mass ratio. :0.5~1:10. The multilayer substrate according to claim 1 or 2, wherein the cationically polymerizable resin has at least one cationically curable functional group selected from the group consisting of an epoxy group and an oxetanyl group. The multilayer substrate of claim 1 or 2, wherein the radical polymerizable resin Contains: a polyfunctional (meth) acrylate monomer having a hydroxyl group. The multilayer substrate of claim 1 or 2, wherein the protective layer has a thickness of 2 μm or more and less than 20 μm. The multilayer substrate of claim 1 or 2, wherein a thickness ratio of the protective layer to the substrate film is 0.04 to 5. The multilayer substrate of claim 1 or 2 has a total thickness of 23 to 70 μm. The multilayer substrate of claim 1 or 2, wherein the substrate film is selected from the group consisting of a triacetylcellulose film, a polyester film, and an acrylic film. The multilayer substrate according to claim 1 or 2, wherein the multilayer substrate is cut into 100 mm × 100 mm and the shortest distance between the ends of the multilayer substrate when placed on a horizontal surface is 60 to 100 mm. An image display device comprising the multilayer substrate of claim 1 or 2.