JP2019044136A - Composition for primer layer formation, barrier film, wavelength conversion sheet, and method for producing wavelength conversion sheet - Google Patents

Abstract

To provide a composition for primer layer formation capable of forming a primer layer capable of obtaining excellent adhesion to a phosphor layer.SOLUTION: A composition for primer layer formation for forming a primer layer adjacent to a phosphor layer of an optical laminate contains a polyfunctional compound and a curing agent, where the polyfunctional compound has a functional group A having reactivity or intermolecular force bondability to a curable resin used for the phosphor layer and a functional group B which is the same as or different from the functional group A and has reactivity to the curing agent, at the terminal of a main chain or a side chain of a resin skeleton, the functional group B contains at least one functional group selected from the group consisting of a hydroxyl group, a vinyl group, an acryloyl group, a methacryloyl group, a silanol group, an amino group and a carboxyl group, and the curing agent contains an isocyanurate type compound.SELECTED DRAWING: None

Description

  The present invention relates to a composition for forming a primer layer, a barrier film, a wavelength conversion sheet, and a method for producing a wavelength conversion sheet.

  A wavelength conversion sheet using a phosphor such as quantum dots has high luminance and color reproducibility, and its adoption in displays is desired. However, phosphors such as quantum dots are degraded by contact with oxygen or water vapor. Therefore, the wavelength conversion sheet often adopts a structure in which a barrier film in which a gas barrier layer is formed on a polymer film is disposed on one side or both sides of a phosphor layer containing a phosphor.

  For example, in patent document 1, permeation of oxygen etc. to a fluorescent substance layer is prevented by bonding a barrier film together on both surfaces of the fluorescent substance layer which disperse | distributed the quantum dot to acrylic resin and an epoxy resin.

International Publication No. 2014/113562

  However, the phosphor layer in which the quantum dots, which are inorganic materials, as described in Patent Document 1 are dispersed has poor adhesion to the barrier film, and there is a risk that peeling may occur between the phosphor layer and the barrier film. there were. In addition, not only the quantum dot film as described in Patent Document 1 but also an optical laminate having a structure in which a phosphor layer and a barrier film are laminated, peeling of the barrier film has a great effect on the performance decrease. There is a need to improve the adhesion between the barrier film and the phosphor layer.

  The present invention has been made in view of the problems of the prior art, and a composition for forming a primer layer capable of forming a primer layer capable of obtaining excellent adhesion to a phosphor layer, and formed using the composition It is an object of the present invention to provide a barrier film provided with the primer layer, a wavelength conversion sheet provided with the barrier film, and a method for producing a wavelength conversion sheet.

  In order to achieve the above object, the present invention is a composition for forming a primer layer for forming a primer layer adjacent to a phosphor layer of an optical laminate, which comprises a polyfunctional compound and a curing agent. The multifunctional compound has a functional group A having reactivity or intermolecular force bonding property with the curable resin used in the phosphor layer at the end of the main chain or side chain of the resin skeleton, and the functional group The functional group B which is the same as or different from the group A and has reactivity with the curing agent, and the functional group B is a hydroxyl group, a vinyl group, an acryloyl group, a methacryloyl group, a silanol group, an amino group and a carboxyl group A composition for forming a primer layer, comprising at least one functional group selected from the group consisting of and wherein the curing agent comprises an isocyanurate type compound.

  According to the composition for forming a primer layer, a primer having excellent adhesion to a phosphor layer can be obtained by containing the polyfunctional compound having the specific functional group and an isocyanurate type compound as a curing agent. Layers can be formed. It is believed that the above excellent adhesion can be obtained due to the following reasons. That is, the polyfunctional compound not only has a functional group B for reacting and curing with the curing agent, but also a functionality having reactivity or intermolecular force bonding to the curable resin used in the phosphor layer. By having the group A, the adhesion to the phosphor layer can be improved. Further, by using an isocyanurate type compound as a curing agent, the adhesion between the primer layer and the phosphor layer can be improved as compared with the case where a curing agent having no isocyanurate skeleton is used. An isocyanurate type curing agent is often used as a curing agent for a curable resin used for the phosphor layer, for the reasons of reactivity, weatherability, and improvement of crosslink density. In the case of forming a phosphor layer using such an isocyanurate type curing agent, in particular, since the affinity between the curing agent used for this phosphor layer and the curing agent used for the primer layer becomes high, the adhesion is improved. It can be greatly improved. On the other hand, although the reason is not clear, even when a curing agent having no isocyanurate skeleton is used in the phosphor layer, the isocyanurate skeleton is used in the primer layer by using an isocyanurate type compound in the primer layer. The adhesion between the primer layer and the phosphor layer can be improved as compared with the case of using a curing agent not having the above. Furthermore, by using the polyfunctional compound having the above-mentioned structure, the functional group A is uniformly present in the composition for forming a primer layer and the primer layer formed using the same, and stable adhesion can be obtained. it can. By forming a primer layer in the outermost surface of the barrier film of the side which contact | connects a fluorescent substance layer using this composition for primer layer formation, peeling of a barrier film can be suppressed.

  In the composition for forming a primer layer, the isocyanurate type compound is preferably an aliphatic isocyanurate type compound. When an aliphatic isocyanurate type compound is used as the isocyanurate type compound, yellowing of the primer layer with time can be suppressed and the appearance can be made better than when an aromatic isocyanurate type compound is used.

  In the composition for forming a primer layer, the functional group A and the functional group B are preferably different functional groups. Because the functional group A and the functional group B are different functional groups, the functional group B mainly bears the curing reaction with the curing agent, and the functional group A bears mainly the adhesion improvement of the primer layer to the phosphor layer Since roles can be shared, good reactivity between the polyfunctional compound and the curing agent, and excellent adhesion between the primer layer and the phosphor layer can be stably obtained.

  The present invention also provides a barrier film comprising a gas barrier film and a primer layer, which is disposed on one outermost surface and is a cured product of the composition for forming a primer layer of the present invention.

  According to the barrier film, by providing the primer layer, excellent adhesion to the phosphor layer can be obtained through the primer layer.

  The present invention also includes a phosphor layer containing a cured product of a phosphor and a curable resin, and the barrier film of the present invention laminated on at least one surface of the phosphor layer, the barrier film comprising A wavelength conversion sheet comprising the primer layer on the outermost surface of the phosphor layer side.

  According to the wavelength conversion sheet, excellent adhesion between the barrier film and the phosphor layer can be obtained by laminating the barrier film and the phosphor layer via the primer layer.

  The present invention further provides fluorescence on the above-mentioned primer layer of a barrier film provided with a gas barrier film and a primer layer composed of a cured product of the composition for forming a primer layer of the above-mentioned present invention disposed on one outermost surface. A step of applying a composition for forming a phosphor layer containing a body and a curable resin to form a coated film, and a step of curing the curable resin in the coated film to form a phosphor layer Provided is a method for producing a wavelength conversion sheet.

  In the wavelength conversion sheet obtained by the above method, excellent adhesion between the barrier film and the phosphor layer can be obtained by laminating the barrier film and the phosphor layer via the primer layer.

  According to the present invention, a composition for forming a primer layer capable of forming a primer layer capable of obtaining excellent adhesion to a phosphor layer, a barrier film provided with a primer layer formed using the same, and the barrier film The wavelength conversion sheet provided, and the manufacturing method of a wavelength conversion sheet can be provided.

It is a schematic cross section which shows one Embodiment of the barrier film of this invention. It is a schematic cross section which shows one Embodiment of the barrier film of this invention. It is a schematic cross section which shows one Embodiment of the barrier film of this invention. It is a schematic cross section which shows one Embodiment of the barrier film of this invention. It is a schematic cross section which shows one Embodiment of the barrier film of this invention. It is a schematic cross section which shows one Embodiment of the wavelength conversion sheet | seat of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as needed. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and overlapping descriptions will be omitted. Further, the dimensional ratio in the drawings is not limited to the illustrated ratio.

[Composition for forming primer layer]
The composition for forming a primer layer of the present invention is a composition for forming a primer layer for forming a primer layer adjacent to a phosphor layer of an optical laminate, and contains a polyfunctional compound and a curing agent, The multifunctional compound has a functional group A having reactivity or intermolecular bondability with the curable resin used in the phosphor layer at the main chain or side chain end of the resin skeleton, and the functional group A functional group B having reactivity with the curing agent which is the same as or different from A, and the functional group B is selected from a hydroxyl group, a vinyl group, an acryloyl group, a methacryloyl group, a silanol group, an amino group and a carboxyl group The curing agent contains at least one functional group selected from the group consisting of isocyanurate type compounds. Each component will be described in detail below.

(Multifunctional compound)
In the polyfunctional compound, the resin skeleton having the functional group A and the functional group B in the main chain or side chain is preferably derived from a polyester resin and / or an acrylic resin. The polyester resin and the acrylic resin may be linear or branched. As polyester resin, polyester resin which has a carboxyl group and a hydroxyl group at an end is generally mentioned. In addition, polyester resins using trimethylolpropane, neopentyl glycol, etc. as copolymerization components, and polyester resins using pyromellitic acid, trimellitic acid, etc. introduce a hydroxyl group or a carboxyl group to the side chain. It becomes possible to provide reactivity not only to the end but also to the side chain. In the case of an acrylic resin, it is possible to introduce a hydroxyl group or a carboxyl group to the side chain by using acrylic acid, methacrylic acid, hydroxyethyl methacrylate or the like as a copolymerization component. In addition, the acrylic resin may have an amino group introduced in the main chain or side chain.

  The resin skeleton of the polyfunctional compound is preferably derived from a polyol such as polyester polyol, acrylic polyol, polycarbonate polyol, polyether polyol, polydiene polyol etc., and is derived from polyester polyol or acrylic polyol Is more preferred.

  The functional group A is a functional group having reactivity or intermolecular bondability to the curable resin used in the phosphor layer. Specific examples of the functional group A include a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a mercapto group, a vinyl group, an acryloyl group and a methacryloyl group, and the like, and is selected according to the type of the curable resin. The functional group A may be of one type, or of two or more types.

  When the curable resin used for the phosphor layer is an acrylic photocurable resin, ethylenic divinyl compounds such as vinyl group, acryloyl group and methacryloyl group can be used as the functional group A at the end of the main chain or side chain of the polyfunctional compound. It is preferable to have a group having a heavy bond or a mercapto group. When the curable resin is an epoxy-based cationic photopolymerizable resin or an epoxy-amine-based thermosetting resin, an amino group, a carboxyl group, an epoxy group as a functional group A at the end of the main chain or side chain of the polyfunctional compound Alternatively, it is preferable to have a mercapto group. When the curable resin is a urethane-curable thermosetting resin, a functional group having polarity such as a hydroxyl group, a carbonyl group or an amino group as a functional group A is provided at the end of the main chain or side chain of the polyfunctional compound. Is preferred. Thus, the adhesion between the primer layer and the phosphor layer can be enhanced by selecting the functional group A according to the type of the curable resin used for the phosphor layer.

  The functional group A is at least one type of curing selected from the group consisting of an acrylic photocurable resin, an epoxy photocationically polymerizable resin, an epoxy-amine thermosetting resin, and a urethane curing thermosetting resin. It can also be said that it is a group having reactivity or intermolecular bondability to a resin. Further, it can be said that the functional group A is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a mercapto group, a vinyl group, an acryloyl group and a methacryloyl group. And at least one functional group selected from the group consisting of an epoxy group, an amino group, a mercapto group, a vinyl group, an acryloyl group, and a methacryloyl group, and a carboxyl group, an epoxy group, an amino group, a mercapto group And at least one functional group selected from the group consisting of vinyl, acryloyl and methacryloyl groups.

  The functional group B is a functional group having reactivity with the curing agent in the composition for forming a primer layer. The functional group B contains at least one functional group selected from the group consisting of a hydroxyl group, a vinyl group, an acryloyl group, a methacryloyl group, a silanol group, an amino group and a carboxyl group. The functional group B is selected from the above-mentioned functional groups according to the type of curing agent. The functional group B may be of one type, or of two or more types. The functional group B may be the same as or different from the functional group A.

  In the composition for forming a primer layer of the present embodiment, a functional group A from the viewpoint of stably obtaining excellent reactivity between the polyfunctional compound and the curing agent and excellent adhesion between the primer layer and the phosphor layer. And functional group B are preferably different. In this case, the functional group A is preferably a functional group having no reactivity with the curing agent in the composition for forming a primer layer. Since the functional group A does not have reactivity with the curing agent, unreacted functional group A remains in the primer layer after curing, and stable adhesion to the phosphor layer is stabilized. You can get it.

  The functional group A and the functional group B may be the same, in which case the polyfunctional compound has reactivity or intermolecular force bonding to the curable resin used in the phosphor layer, In addition, it is sufficient to have one type of functional group having reactivity with the curing agent used in the composition for forming a primer layer. Such compounds have the advantage that their preparation is easy. When such a compound is used, a part of functional groups can be left in the primer layer after curing by adjusting the amount of the curing agent added to the composition for forming a primer layer, and the remaining functional groups Thus, the adhesion to the phosphor layer can be improved.

  The functional group equivalent (weight of the compound containing one equivalent of the functional group) of the functional group A in the polyfunctional compound is 100 to 20 000 g / eq from the viewpoint of obtaining better adhesion to the phosphor layer Is preferable, 200 to 10000 g / eq is more preferable, and 300 to 5000 g / eq is particularly preferable. The functional group equivalent of the functional group B in the polyfunctional compound is preferably 100 to 20000 g / eq, more preferably 200 to 10000 g / eq, from the viewpoint of obtaining good reactivity with the curing agent. It is particularly preferred that it is 300 to 5000 g / eq.

  The weight average molecular weight of the polyfunctional compound is preferably 500 to 1,000,000, more preferably 1,000 to 500,000, and particularly preferably 1,000 to 100,000. When the weight average molecular weight is 500 or more, the film forming property tends to be good, and when it is 1,000,000 or less, the coating suitability tends to be good. In addition, in this specification, a weight average molecular weight is measured by gel permeation chromatography (GPC), and is calculated | required by converting by the analytical curve using standard polystyrene.

  The polyfunctional compound has a structure in which a functional group B is bonded to a side chain of a resin skeleton having a functional group A in the main chain or side chain, or a side chain of a resin skeleton having a functional group B in the main chain or side chain , May have a structure in which a functional group A is bonded. The above-mentioned structure of the polyfunctional compound can be confirmed, for example, by analysis by FTIR. In the multifunctional compound, the functional group A or the functional group B may be bonded to the side chain of the resin skeleton via a urethane bond and a siloxane bond, and such a structure is also confirmed by analysis by FTIR. be able to.

  The polyfunctional compound having the above structure can be produced, for example, by the following method. That is, in the polyfunctional compound having the above structure, the resin (A) having the functional group A in the main chain or side chain and the compound (B) having the functional group B are reacted to form the functional group A as a main chain Alternatively, it can be produced through the step of obtaining a polyfunctional compound having a structure in which a functional group B is bonded to a side chain of a resin skeleton having a side chain (first embodiment). This method is a method in which the resin (A) and the compound (B) are directly reacted.

  Further, the polyfunctional compound having the above structure comprises a resin (A) having a functional group A in the main chain or side chain and a compound (B) having a functional group B as the resin (A) and the above compound ( A compound (C) which reacts with both of B) is reacted to obtain a polyfunctional compound having a structure in which a functional group B is bonded to a side chain of a resin skeleton having a functional group A in the main chain or side chain. It can manufacture through a process (2nd embodiment). This method is a method in which the compound (B) is bound to the resin (A) via the compound (C) by reacting the compound (C) with the resin (A) and the compound (B). In the first and second embodiments, when obtaining a polyfunctional compound having a structure in which the functional group A is bonded to the side chain of the resin skeleton having the functional group B in the main chain or side chain, the functional group B is mainly used. A resin (A) having a chain or a side chain and a compound (B) having a functional group A may be used.

  More specifically, examples of the method according to the second embodiment include the following methods. That is, the polyfunctional compound having the above structure comprises a resin having two or more hydroxyl groups as the above resin (A) as the functional group B, and a silane coupling agent having the isocyanate group as the above compound (C) A step of obtaining a reaction product by reacting in the reaction (hereinafter referred to as "first step"), reacting the reaction product with a silane coupling agent having a functional group A as the compound (B) Through the step of obtaining the polyfunctional compound (hereinafter referred to as "the second step") (third embodiment). According to this method, it is possible to obtain a polyfunctional compound having a structure in which the functional group A is bonded to the side chain of the resin skeleton having the functional group B in the main chain or side chain via a urethane bond and a siloxane bond. it can.

  As said resin (A) used by the method concerning 1st and 2nd embodiment, polyester-type resin, acrylic resin, etc. which have functional group A or functional group B in a principal chain or a side chain are mentioned.

  The weight average molecular weight of the resin (A) is preferably 500 to 1,000,000, more preferably 1,000 to 500,000, and particularly preferably 1,000 to 100,000. When the weight average molecular weight is 500 or more, the film forming property tends to be improved, and when it is 1,000,000 or less, the coating suitability tends to be good.

  As said compound (B) used by the method concerning 1st and 2nd embodiment, in addition to the silane coupling agent which has the functional group A used by the method concerning 3rd embodiment, hydroxy system such as hydroxyethyl methacrylate etc. Examples thereof include acrylic monomers, isocyanate-based acrylic monomers such as isocyanate ethyl methacrylate, glycidyl-based acrylic monomers such as glycidyl methacrylate, and unsaturated carboxylic acids such as acrylic acid and methacrylic acid.

  As a compound (C) used by the method concerning 2nd embodiment, diisocyanate compounds, such as hexamethylene diisocyanate, etc. other than the silane coupling agent which has an isocyanate group used by the method concerning 3rd embodiment are mentioned.

  The reaction of the resin (A) with the compound (B) in the method according to the first embodiment and the reaction of the resin (A) with the compound (C) with the compound (B) in the method according to the second embodiment are For example, it can carry out by stirring for 0.5 to 24 hours at 10-80 degreeC in solvent, such as ethyl acetate, toluene, methyl ethyl ketone. Thereby, functional group A or B is introduce | transduced to the side chain of resin (A).

  Next, a method according to the third embodiment will be described.

  In the first step, the resin having two or more hydroxyl groups is preferably a polyol such as polyester polyol, acrylic polyol, polycarbonate polyol, polyether polyol, polydiene polyol, etc., and polyester polyol or acrylic polyol is more preferable. preferable.

  From the viewpoint of reactivity, the hydroxyl value of the polyol used in the first step is preferably 0.1 to 5000 mg KOH / g, and more preferably 1 to 1000 mg KOH / g.

  The weight average molecular weight of the polyol used in the first step is preferably 500 to 1,000,000, more preferably 1,000 to 500,000, and particularly preferably 1,000 to 100,000. When the weight average molecular weight is 500 or more, the film forming property tends to be improved, and when it is 1,000,000 or less, the coating suitability tends to be good.

  In the first step, examples of the silane coupling agent having an isocyanate group include 3-isocyanatopropyltriethoxysilane and the like.

  In the first step, the reaction between the resin having two or more hydroxyl groups and the silane coupling agent having an isocyanate group is carried out, for example, in a solvent such as ethyl acetate, toluene, methyl ethyl ketone or the like at 0.5 to 80 ° C. It can carry out by stirring for 24 hours. As a result, the hydroxyl group of the resin and the isocyanate group of the silane coupling agent react to form a urethane bond, and the silane coupling agent is introduced to the side chain of the resin skeleton.

  In the second step, examples of the functional group A of the silane coupling agent having a functional group A include a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a mercapto group, a vinyl group, an acryloyl group and a methacryloyl group. The functional group A may be of one type, or of two or more types. In addition, as this silane coupling agent, two or more types of silane coupling agents having different functional groups may be used in combination.

  In the second step, the reaction of the reaction product obtained in the first step with the silane coupling agent having a functional group A is carried out, for example, in a solvent such as ethyl acetate, toluene, methyl ethyl ketone or the like at 10 to 80 ° C. The reaction can be carried out by stirring for 0.5 to 24 hours. Thus, the alkoxysilane moiety of the silane coupling agent introduced to the side chain of the reaction product obtained in the first step and the alkoxysilane moiety of the silane coupling agent having the functional group A are hydrolyzed and condensed. Form a siloxane bond. As a result, it is possible to obtain a polyfunctional compound having a structure in which the functional group A is pendantly bonded to the side chain of the resin skeleton via the urethane bond and the siloxane bond.

  The content of the polyfunctional compound in the composition for forming a primer layer is preferably 5 to 100% by mass, based on the total solid content of the composition for forming a primer layer, and is 10 to 100% by mass. It is more preferable, and it is especially preferable that it is 10-99 mass%. When the content is 5% by mass or more, adhesion tends to be improved.

(Hardening agent)
The curing agent comprises an isocyanurate type compound capable of curing the multifunctional compound. Examples of the isocyanurate type compounds include aliphatic isocyanurate type compounds and aromatic isocyanurate type compounds. Among these, aliphatic isocyanurate type compounds are preferable from the viewpoint of suppressing yellowing of the primer layer with time. Here, the aliphatic isocyanurate type compound means a chain aliphatic isocyanurate type compound and an alicyclic isocyanurate type compound. The linear aliphatic isocyanurate type compound may be a linear aliphatic isocyanurate type compound or may be a branched aliphatic isocyanurate type compound. As a functional group contained in the curing agent to react with the polyfunctional compound, isocyanate group, allyl group, silanol group, epoxy group etc. may be mentioned, and among these, the kind of functional group B of the polyfunctional compound It is appropriately selected accordingly.

  Examples of the isocyanurate compound include isocyanurate compounds obtained by trimerizing a diisocyanate compound such as hexamethylene diisocyanate, triallyl isocyanurate, tris- (trimethoxysilylpropyl) isocyanurate, triglycidyl isocyanurate and the like.

  When the functional group B contained in the polyfunctional compound is a hydroxyl group, it is preferable to use a compound having a polyfunctional isocyanate group as the curing agent. When the functional group B contained in the polyfunctional compound is a vinyl group, an acryloyl group or a methacryloyl group, it is preferable to use a compound having a polyfunctional allyl group as the curing agent. When the functional group B contained in the polyfunctional compound is a silanol group, it is preferable to use a compound having a polyfunctional amino group or a silane coupling agent as the curing agent. When the functional group B contained in the polyfunctional compound is an amino group or a carboxyl group, it is preferable to use a compound having a polyfunctional epoxy group as the curing agent.

  In the composition for forming a primer layer, the content of the isocyanurate type compound as a curing agent is preferably 0.01 to 95% by mass, based on the total solid content of the composition for forming a primer layer, and 0. The content is more preferably 1 to 80% by mass, and particularly preferably 1 to 50% by mass. When the content exceeds 95% by mass, the film tends to be brittle, and when it is less than 0.01% by mass, the film after film formation tends to be too soft.

  By blending the above-mentioned curing agent with the composition for forming a primer layer, the primer layer to be formed can not only improve the adhesion to the phosphor layer or various substrates (barrier film side), but also high temperature and humidity (for example, Even in a severe environment where long-term reliability such as 85 ° C. and 85% RH is required, it is possible to maintain good adhesion.

  The composition for forming a primer layer may contain other components (additives) other than the above-described polyfunctional compound and the curing agent. Examples of the additive include a slip agent, a surfactant, a dilution solvent, an antifoaming agent, an antistatic agent and the like.

[Method of producing composition for forming primer layer]
The method for producing a composition for forming a primer layer of the present invention is a method comprising the step of producing a polyfunctional compound by the method according to the first to third embodiments described above.

  The method for producing the composition for forming a primer layer may further include the step of blending a curing agent with the polyfunctional compound. In addition, in such a step, other additives other than the curing agent can be added as needed.

  Through the above steps, a composition for forming a primer layer can be obtained.

[Barrier film]
The barrier film of the present invention comprises a gas barrier film and a primer layer which is disposed on one outermost surface of the barrier film and which is a cured product of the composition for forming a primer layer. Hereinafter, preferred embodiments of the barrier film of the present invention will be described using the drawings.

  FIGS. 1-5 is a schematic cross section which shows one Embodiment of the barrier film of this invention. The barrier film 100 shown in FIG. 1 includes a first film 1 which is a gas barrier film, a second film 2 which is a gas barrier film, an adhesive layer 4, a primer layer 5 and a mat layer 6. Here, the first film 1 is provided with a first base 11, an anchor coat layer 12, and a barrier layer 15 composed of an inorganic thin film layer 13 and a gas barrier coating layer 14. The second film 2 includes a second base 21, an anchor coat layer 22, and a barrier layer 25 composed of an inorganic thin film layer 23 and a gas barrier coating layer 24. The first film 1 and the second film 2 are bonded via the adhesive layer 4 so that the gas barrier coating layer 14 and the gas barrier coating layer 24 face each other. In the barrier film 100, the primer layer 5 is disposed on the surface of the first film 1 on the first substrate 11 side in a state of being in contact with the first substrate 11, and the mat layer 6 is It is arrange | positioned in the state which contact | connected the 2nd base material 21 on the surface at the side of the 2nd base material 21 of the film 2 of 2. FIG. Since the barrier film 100 having the structure shown in FIG. 1 has two gas barrier films of the first and second films 1 and 2 bonded to each other, the permeation of moisture and oxygen can be sufficiently suppressed. . In addition, by arranging the barrier layers 15 and 25 inside the first and second substrates 11 and 21, the barrier layers 15 and 25 are protected, and damage to the barrier layers 15 and 25 is suppressed.

  The barrier film 200 shown in FIG. 2 includes a first film 1 which is a gas barrier film, a second film 2 which is a gas barrier film, an adhesive layer 4, a primer layer 5 and a mat layer 6. Here, the first film 1 is provided with a first base 11, an anchor coat layer 12, and a barrier layer 15 composed of an inorganic thin film layer 13 and a gas barrier coating layer 14. The second film 2 includes a second base 21, an anchor coat layer 22, and a barrier layer 25 composed of an inorganic thin film layer 23 and a gas barrier coating layer 24. The first film 1 and the second film 2 are pasted together via the adhesive layer 4 so that the first base 11 and the gas barrier coating layer 24 face each other. In the barrier film 200, the primer layer 5 is disposed on the surface of the first film 1 on the gas barrier coating layer 14 side in a state of being in contact with the gas barrier coating layer 14; It is arrange | positioned in the state which contact | connected the 2nd base material 21 on the surface at the side of the 2nd base material 21 of the film 2. As shown in FIG. Since the barrier film 200 having the structure shown in FIG. 2 has the two gas barrier films of the first and second films 1 and 2 attached to each other, the permeation of moisture and oxygen can be sufficiently suppressed. . Further, by disposing the barrier layer 15 on the primer layer 5 side, that is, at a position closer to the phosphor layer, it is possible to more sufficiently suppress the entry of moisture and oxygen into the phosphor layer.

  The barrier film 300 shown in FIG. 3 includes a first film 1 which is a gas barrier film, a second film 2, an adhesive layer 4, a primer layer 5, and a mat layer 6. Here, the first film 1 includes the first base material 11, the anchor coat layer 12, and the barrier layer 15 formed by alternately laminating two layers of the inorganic thin film layer 13 and the gas barrier coating layer 14. ing. The second film 2 is composed of only the second base 21. The first film 1 and the second film 2 are pasted together via the adhesive layer 4 so that the gas barrier coating layer 14 and the second base 21 face each other. In the barrier film 300, the primer layer 5 is disposed on the surface of the first film 1 on the side of the first substrate 11 in a state of being in contact with the first substrate 11, and the mat layer 6 is It is arrange | positioned in the state which contact | connected the 2nd base material 21 on the surface on the opposite side to the contact bonding layer 4 of the 2nd base material 21 which comprises the film 2 of 2. FIG. In the barrier film 300 having the structure shown in FIG. 3, the second film 2 is configured only with the second base material 21, so simplification of the manufacturing process and cost reduction can be achieved. In addition, since the barrier layer 15 has a structure in which the inorganic thin film layer 13 and the gas barrier coating layer 14 are alternately laminated in two layers, the gas barrier properties can be enhanced.

  The barrier film 400 shown in FIG. 4 includes a first film 1 which is a gas barrier film, a primer layer 5 and a mat layer 6. Here, the first film 1 includes the first base material 11, the anchor coat layer 12, and the barrier layer 15 formed by alternately laminating two layers of the inorganic thin film layer 13 and the gas barrier coating layer 14. ing. In the barrier film 300, the primer layer 5 is disposed on the surface of the first film 1 on the side of the gas barrier coating layer 14 in a state of being in contact with the first substrate 11, and the mat layer 6 is The second substrate 21 constituting the film 2 is disposed in contact with the second substrate 21 on the surface opposite to the adhesive layer 4 of the second substrate 21. Since the barrier film 400 having the structure shown in FIG. 4 does not include the second film 2 and the adhesive layer 4, simplification of the manufacturing process, cost reduction and thickness reduction can be achieved. In addition, since the barrier layer 15 has a structure in which the inorganic thin film layer 13 and the gas barrier coating layer 14 are alternately laminated in two layers, the gas barrier properties can be enhanced.

  The barrier film 500 shown in FIG. 5 includes a first film 1 which is a gas barrier film, a second film 2 which is a gas barrier film, a third film 3, two adhesive layers 4, and a primer layer 5. And the mat layer 6. Here, the first film 1 is provided with a first base 11, an anchor coat layer 12, and a barrier layer 15 composed of an inorganic thin film layer 13 and a gas barrier coating layer 14. The second film 2 includes a second base 21, an anchor coat layer 22, and a barrier layer 25 composed of an inorganic thin film layer 23 and a gas barrier coating layer 24. The third film is composed of only the third base 31. This third film is provided, for example, for thickness adjustment. The first film 1 and the second film 2 are bonded via the adhesive layer 4 so that the gas barrier coating layer 14 and the gas barrier coating layer 24 face each other. The 2nd film 2 and the 3rd film 3 are pasted together via adhesion layer 4 so that the 2nd substrate 21 and the 3rd substrate 31 may be opposite. Furthermore, the mat layer 6 is provided on the third base 31. In the barrier film 500, the primer layer 5 is disposed on the surface of the first film 1 on the side of the first substrate 11 in a state of being in contact with the first substrate 11. Since the barrier film 500 having the structure shown in FIG. 5 has two gas barrier films of the first and second films 1 and 2 attached to each other, the permeation of moisture and oxygen can be sufficiently suppressed. . In addition, by arranging the barrier layers 15 and 25 inside the first and second substrates 11 and 21, the barrier layers 15 and 25 are protected, and damage to the barrier layers 15 and 25 is suppressed.

  The barrier film having the above-described configuration has good gas barrier properties, and can be attached to the phosphor layer via the primer layer 5 to obtain excellent adhesion. Moreover, the primer layer 5 is formed using the composition for primer layer formation containing the polyfunctional compound mentioned above, It is very favorable also with respect to any of the 1st base material 11 and the gas barrier coating layer 14 The adhesive property is exhibited, and the occurrence of peeling in the barrier film is also sufficiently suppressed. Therefore, the barrier film having the above-described configuration can suppress the penetration of oxygen and water vapor from the interface between the barrier film and the phosphor layer, and can suppress the deterioration of the phosphor layer.

  Hereinafter, each layer which comprises a barrier film is demonstrated in detail.

(Base material)
The first, second and third substrates 11, 21 and 31 are preferably polymer films. Examples of the material of the polymer film include polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides such as nylon; polyolefins such as polypropylene and cycloolefin; polycarbonate; and triacetyl cellulose etc. It is not limited to. The polymer film is preferably a polyester film, a polyamide film or a polyolefin film, more preferably a polyester film or a polyamide film, and still more preferably a polyethylene terephthalate film. Polyethylene terephthalate film is desirable from the viewpoint of transparency, processing suitability and adhesion. The polyethylene terephthalate film is preferably a biaxially stretched polyethylene terephthalate film from the viewpoint of transparency and gas barrier properties.

  The polymer film may optionally contain additives such as an antistatic agent, an ultraviolet light absorber, a plasticizer and a slip agent. In addition, the surface of the polymer film may be subjected to corona treatment, flame treatment and plasma treatment.

  In the barrier film, when the first base material 11 and the primer layer 5 are in contact with each other, the first base material 11 preferably has a polar group such as a hydroxyl group on the surface. When the first base material 11 has a polar group such as a hydroxyl group on the surface, the intermolecular force between the polar group such as the hydroxyl group and the functional group in the primer layer 5 further improves the adhesion. Among the above-mentioned polymer films, as the one having a hydroxyl group on the surface, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, a cellulose triacetate film and the like are usually mentioned. Further, adhesion to the primer layer 5 can be further improved by performing surface treatment such as corona treatment, flame treatment and plasma treatment.

  The thickness of the first, second and third substrates 11, 21 and 31 is not particularly limited, but is preferably 3 μm or more and 100 μm or less, and more preferably 5 μm or more and 50 μm or less. Processing is easy as this thickness is 3 micrometers or more, and the total thickness of a barrier film can be made thin as it is 100 micrometers or less.

(Anchor coat layer)
The anchor coat layers 12 and 22 are provided between the first and second substrates 11 and 21 and the inorganic thin film layers 13 and 23 in order to improve the adhesion therebetween. In addition, the anchor coat layers 12 and 22 may have a barrier property to prevent permeation of water and oxygen.

  The anchor coat layers 12 and 22 are, for example, polyester resin, isocyanate resin, urethane resin, acrylic resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, oxazoline group-containing resin, modified styrene resin, modified silicone resin Alternatively, it can be formed using a resin selected from alkyl titanates and the like. The anchor coat layer can be formed using the above-described resin alone or using a composite resin in which two or more of the above-described resins are combined.

  The anchor coat layers 12 and 22 can be formed by applying a solution containing the above-described resin onto the first and second substrates 11 and 21 and drying and curing. As a coating method, the coating method by a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater etc. is mentioned.

  The thickness of the anchor coat layers 12 and 22 is preferably in the range of 5 to 500 nm, and more preferably in the range of 10 to 100 nm. Here, if the thickness is 5 nm or more, the adhesion between the first and second base materials 11 and 21 and the inorganic thin film layers 13 and 23 and the barrier property against moisture and oxygen tend to be improved. If the thickness is 500 nm or less, it tends to be possible to form a uniform layer in which internal stress is sufficiently suppressed.

(Barrier layer)
The barrier layers 15 and 25 are layers provided to further improve the water vapor permeability and the oxygen permeability. It is desirable that the barrier layers 15 and 25 have high transparency from the optical point of view. The barrier layers 15 and 25 may be single-layered or multi-layered, but as shown in FIGS. 1 to 5, it is preferable to have the inorganic thin film layers 13 and 23 and the gas barrier covering layers 14 and 24. .

  The barrier layers 15 and 25 may be formed in the air or in vacuum. Examples of vacuum deposition include physical vapor deposition and chemical vapor deposition. Examples of physical vapor deposition include vacuum deposition, sputtering and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD (PECVD) method, and a photo CVD method. The film forming method may be different between the inorganic thin film layers 13 and 23 and the gas barrier covering layers 14 and 24.

(Inorganic thin film layer)
It is preferable that the formation method of the inorganic thin film layers 13 and 23 is a vacuum evaporation method, sputtering method, or PECVD method. In vacuum deposition, resistance heating vacuum deposition, electron beam heating vacuum deposition, and induction heating vacuum deposition are more preferable, and in sputtering, reactive sputtering and dual magnetron sputtering are used. Is more preferred. Sputtering is preferred from the viewpoint of film homogeneity, and vacuum deposition is preferred from the viewpoint of cost, and can be selected according to the purpose and application.

  As a plasma generation method in the sputtering method and the PECVD method, mention may be made of a DC (Direct Current) method, an RF (Radio Frequency) method, an MF (Middle Frequency) method, a DC pulse method, an RF pulse method, a DC + RF superposition method and the like. Can.

  In vacuum film formation, a film such as a metal or an oxide such as silicon, nitride or nitride oxide is usually formed. The inorganic thin film layers 13 and 23 are preferably films of metals such as aluminum, titanium, copper, indium and tin, or oxides (such as alumina) thereof, or silicon and silicon oxides. In addition to the metal or silicon oxide, a film of metal or silicon nitride or nitride oxide may be formed. Also, a film containing a plurality of metals may be formed. The above-mentioned oxides, nitrides and nitride oxides of aluminum, titanium, copper, indium and silicon are excellent in both transparency and barrier property. Oxides containing silicon and nitride oxides are particularly preferable because of their high barrier properties.

  The thickness of the inorganic thin film layers 13 and 23 formed by vacuum film formation is preferably 5 nm or more and 100 nm or less. If the thickness of the inorganic thin film layers 13 and 23 is 5 nm or more, a better barrier property tends to be obtained. In addition, when the thickness of the inorganic thin film layers 13 and 23 is 100 nm or less, generation of cracks can be suppressed, and deterioration of the water vapor barrier property and oxygen barrier property due to the cracks can be suppressed. Furthermore, if the thickness of the inorganic thin film layers 13 and 23 is 100 nm or less, the cost can be reduced due to the reduction of the amount of material used, the shortening of the film formation time, etc.

(Gas barrier coating layer)
The gas barrier coating layers 14 and 24 are provided to provide high barrier properties while preventing various secondary damage in the later steps. The gas barrier coating layers 14 and 24 may contain a siloxane bond. The gas barrier coating layers 14 and 24 can also be formed in the air. In the case where the gas barrier coating layers 14 and 24 are formed in the atmosphere, for example, polyvinyl alcohol, polyvinyl pyrrolidone, a compound having polarity such as ethylene vinyl alcohol, a compound containing chlorine such as polyvinylidene chloride, and Si atoms are included. A coating solution containing a compound, a compound containing a Ti atom, a compound containing an Al atom, a compound containing a Zr atom, and the like can be applied onto the inorganic thin film layers 13 and 23 and dried and cured.

  Specific examples of the coating method of the coating liquid when forming the gas barrier coating layers 14 and 24 in the air include coating methods using a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, etc. Be

The compound containing a siloxane bond is preferably formed, for example, by reacting a silanol group using a silane compound. As such a silane compound, the compound represented by following formula (1) is mentioned.
R ¹ _n (OR ² ) _4-n Si (1)
[In the formula, n represents an integer of 0 to 3, R ¹ and R ² each independently represent a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms. ]

  Examples of the compound represented by the above formula (1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. Etc. You may use the polysilazane containing nitrogen.

Moreover, you may use the material made from the precursor which consists of another metal atom for gas barrier coating layer 14 and 24. FIG. As a compound containing Ti atom, the compound represented by following formula (2) is mentioned, for example.
R ¹ _n (OR ² ) _4-n Ti (2)
[In the formula, n represents an integer of 0 to 3, R ¹ and R ² each independently represent a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms. ]

  Examples of the compound represented by the above formula (2) include tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium.

As a compound containing Al atom, the compound represented by following formula (3) is mentioned, for example.
R ¹ _m (OR ² ) _3-m Al (3)
Wherein, m represents an integer of 0 to 2, R ¹ and R ² each independently represent a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms. ]

  Examples of the compound represented by the above formula (3) include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, and tributoxyaluminum.

As a compound containing a Zr atom, the compound represented by following formula (4) is mentioned, for example.
R ¹ _n (OR ² ) _4-n Zr (4)
[In the formula, n represents an integer of 0 to 3, R ¹ and R ² each independently represent a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms. ]

  Examples of the compound represented by the above formula (4) include tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, and tetrabutoxyzirconium.

  When the gas barrier coating layers 14 and 24 are formed in the air, the coating solution is cured after coating. The curing method is not particularly limited, and examples thereof include ultraviolet curing and thermal curing. In the case of UV curing, the coating solution may contain a polymerization initiator and a compound having a double bond. Moreover, heat aging may be performed as needed.

  As another method of forming the gas barrier coating layers 14 and 24 in the atmosphere, particles of inorganic oxides such as magnesium, calcium, zinc, aluminum, silicon, titanium, zirconium, etc., intervene through phosphorus atoms derived from phosphorus compounds. It is also possible to use a method in which a reaction product obtained by dehydration condensation is used as a gas barrier coating layer. Specifically, a functional group (for example, a hydroxyl group) present on the surface of an inorganic oxide and a site of a phosphorus compound capable of reacting with the inorganic oxide (for example, a halogen atom directly bonded to a phosphorus atom or a phosphorus atom directly The bonded oxygen atom) causes a condensation reaction to bond. The reaction product is obtained, for example, by applying a coating solution containing an inorganic oxide and a phosphorus compound on the surface of the inorganic thin film layers 13 and 23 and thermally treating the formed coating film, whereby particles of the inorganic oxide It can be obtained by proceeding a reaction of binding via a phosphorus atom derived from a compound. The lower limit of the heat treatment temperature is 110 ° C. or more, preferably 120 ° C. or more, more preferably 140 ° C. or more, and still more preferably 170 ° C. or more. When the heat treatment temperature is low, it is difficult to obtain a sufficient reaction rate, which causes a decrease in productivity. Although the preferable upper limit of the temperature of heat processing changes with kinds etc. of a base material, it is 220 degrees C or less, and it is preferable that it is 190 degrees C or less. The heat treatment can be performed in air, in a nitrogen atmosphere, or in an argon atmosphere, or the like.

  In the case where the gas barrier coating layers 14 and 24 are formed in the air, the coating liquid may further contain a resin unless aggregation or the like occurs. Specifically as said resin, an acrylic resin, a polyester resin, etc. are mentioned. It is preferable that the said coating liquid contains resin with high compatibility with the other material in a coating liquid among these resin.

  The coating liquid may further contain a filler, a leveling agent, an antifoaming agent, an ultraviolet light absorber, an antioxidant, a silane coupling agent, a titanium chelating agent, and the like as required.

  The thickness of the gas barrier coating layers 14 and 24 formed in the air is preferably 50 nm to 2000 nm, and more preferably 100 nm to 1000 nm, as the thickness after curing. When the thickness of the gas barrier coating layers 14 and 24 formed in the air is 50 nm or more, the film formation tends to be facilitated. When the thickness of the gas barrier coating layers 14 and 24 formed in the atmosphere is 2000 nm or less, cracking or curling tends to be suppressed.

(Adhesive layer)
The adhesive layer 4 is, as shown in FIGS. 1 to 3 and FIG. 5, the first film 1 and the second film 2 in order to bond and laminate the first film 1 and the second film 2. Provided between the The adhesive layer 4 is also provided when the second film 2 and the third film 3 are bonded to each other as shown in FIG. As the adhesive layer 4, a general one can be used as an adhesive or a pressure-sensitive adhesive for a polymer film, and it is appropriately selected according to the surface on which the first film 1 and the second film 2 are to be bonded. Be done. As a candidate for the material of the adhesive layer 4, an adhesive, an adhesive, or the like such as epoxy type, polyester type, acrylic type, rubber type, phenol type and urethane type can be mentioned.

  Examples of the method for applying the adhesive or the pressure-sensitive adhesive include a method using a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or the like.

  The thickness of the adhesive layer 4 is preferably 1 μm or more and 20 μm or less. When the thickness of the adhesive layer 4 is 1 μm or more, sufficient adhesiveness tends to be obtained, and when it is 20 μm or less, the total thickness of the barrier film can be thinned and the cost increase can be suppressed. is there.

  Moreover, after bonding the 1st film 1 and the 2nd film 2 and the 2nd film 2 and the 3rd film 3 through the contact bonding layer 4, it can age. Aging is performed, for example, at 20 to 80 ° C. for 1 to 10 days.

  The adhesive layer 4 may contain a curing agent, an antistatic agent, a silane coupling agent, an ultraviolet absorber, an antioxidant, a leveling agent, a dispersing agent, and the like, as necessary.

(Primer layer)
The primer layer 5 is a layer provided to improve the adhesion between the barrier film and the phosphor layer. The primer layer 5 is provided on the first substrate 11 of the first film 1 or on the gas barrier coating layer 14. The primer layer 5 is provided on one outermost surface of the barrier film, and the surface of the barrier film on the primer layer 5 side is bonded to the phosphor layer.

  The primer layer 5 is a layer made of a cured product of the composition for forming a primer layer described above. The primer layer 5 can be formed by applying and curing a composition for forming a primer layer on the first substrate 11 of the first film 1 or the gas barrier coating layer 14. As a coating method, the coating method by a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater etc. is mentioned. Curing can be performed, for example, at 60 to 150 ° C. for 15 to 300 seconds.

  The thickness of the primer layer 5 is preferably 0.001 to 10 μm, more preferably 0.01 to 5 μm, still more preferably 0.02 to 3 μm, and 0.05 to 1.5 μm. Is particularly preferred. When the thickness is 0.001 μm or more, the film forming property after coating is stable, and good adhesion can be obtained uniformly in the surface. On the other hand, when the thickness is 10 μm or less, the primer layer 5 can be prevented from becoming brittle and stable adhesion with the phosphor layer can be obtained, and the end of the primer layer 5 (barrier film and phosphor layer) And the infiltration of water vapor and oxygen can be sufficiently suppressed. In addition, when the thickness of the primer layer 5 is smaller, the curing reaction of the primer layer 5 proceeds faster, and the initial adhesion to the phosphor layer becomes better.

(Mat layer)
The matte layer 6 is provided on the surface of the barrier film opposite to the primer layer 5 in order to exert one or more optical functions and an antistatic function. Here, the optical function is not particularly limited, and examples thereof include an interference fringe (moire) prevention function, an antireflection function, and a diffusion function. Among these, the mat layer 6 preferably has at least an interference fringe prevention function as an optical function. In the present embodiment, the case where the mat layer 6 has at least an interference fringe prevention function will be described.

  The mat layer 6 may be configured to include a binder resin and fine particles. Then, the fine particles may be embedded in the binder resin so that a part of the fine particles is exposed from the surface of the mat layer 6, whereby fine irregularities may be generated on the surface of the mat layer 6. By providing such a matte layer 6 on the surface of the barrier film, the generation of interference fringes such as a Newton ring can be sufficiently prevented, and as a result, a wavelength conversion sheet with high efficiency, high definition and long life can be obtained. It becomes possible.

  The binder resin is not particularly limited, but a resin excellent in optical transparency can be used. More specifically, for example, polyester resin, acrylic resin, acrylic urethane resin, polyester acrylate resin, polyurethane acrylate resin, urethane resin, epoxy resin, polycarbonate resin, polyamide resin, polyimide resin Thermoplastic resins such as melamine resins and phenol resins, thermosetting resins, ionizing radiation curable resins, and the like can be used. In addition to the organic resin, a silica binder can also be used. Among these, it is preferable to use an acrylic resin or a urethane resin because of the wideness of the material, and it is more preferable to use an acrylic resin because it is excellent in light resistance and optical properties. These may be used alone or in combination of two or more.

  The fine particles are not particularly limited, but, for example, inorganic particles such as silica, clay, talc, calcium carbonate, calcium sulfate, barium sulfate, barium sulfate, titanium oxide, and alumina, styrene resin, urethane resin, silicone resin, Organic fine particles such as acrylic resin and polyamide resin can be used. Among these, as fine particles, fine particles having a refractive index of 1.40 to 1.55 made of silica, an acrylic resin, a urethane resin, a polyamide resin or the like are preferable in view of transmittance. Fine particles with a low refractive index are expensive, while fine particles with a too high refractive index tend to impair the transmission. These may be used alone or in combination of two or more.

  It is preferable that it is 0.1-30 micrometers, and, as for the average particle diameter of microparticles | fine-particles, it is more preferable that it is 0.5-10 micrometers. When the average particle diameter of the fine particles is 0.1 μm or more, an excellent interference fringe preventing function tends to be obtained, and when it is 30 μm or less, the transparency tends to be further improved.

  The content of the fine particles in the mat layer 6 is preferably 0.5 to 30% by mass, and more preferably 3 to 10% by mass, based on the total amount of the mat layer 6. When the content of the fine particles is 0.5% by mass or more, the light diffusion function and the effect of preventing the generation of interference fringes tend to be further improved, and when the content is 30% by mass or less, the luminance is not reduced. .

  The mat layer 6 can be formed by applying a coating solution containing the binder resin and the fine particles described above on the surface of the first film 1 or the second film 2 and drying and curing. As a coating method, the coating method by a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater etc. is mentioned.

  The thickness of the mat layer 6 is preferably 0.1 to 20 μm, and more preferably 0.3 to 10 μm. When the thickness of the matte layer 6 is 0.1 μm or more, a uniform film tends to be easily obtained, and the optical function tends to be sufficiently obtained. On the other hand, when the thickness of the matting layer 6 is 20 μm or less, when the fine particles are used for the matting layer 6, the fine particles are exposed on the surface of the matting layer 6, and the unevenness imparting effect tends to be easily obtained.

  The barrier film of the present embodiment having the configuration described above can be used for applications requiring a barrier property with respect to permeation of oxygen and water vapor, and for example, a wavelength conversion sheet containing a light emitter used for a liquid crystal backlight Particularly, it can be used as a barrier film of a wavelength conversion sheet containing a quantum dot light emitter.

[Wavelength conversion sheet]
Next, the wavelength conversion sheet of the present invention using the barrier film will be described. The wavelength conversion sheet of the present invention comprises a phosphor layer containing a phosphor and the barrier film of the present invention laminated on at least one surface of the phosphor layer, and the barrier film comprises The primer layer is provided on the outermost surface on the phosphor layer side. FIG. 6 is a schematic cross-sectional view showing an embodiment of the wavelength conversion sheet of the present invention. The wavelength conversion sheet 600 shown in FIG. 6 has a structure in which a phosphor layer 7 having a wavelength conversion function including a phosphor is sandwiched between a pair of barrier films 100. The pair of barrier films 100 and the phosphor layer 7 are laminated such that the primer layer 5 is in contact with the phosphor layer 7. Since the barrier film 100 and the fluorescent substance layer 7 are bonded together through the primer layer 5, the wavelength conversion sheet 600 which has this structure can obtain excellent adhesion. The barrier film 100 may be the barrier film 200, the barrier film 300, or the barrier film 400 described above.

(Phosphor layer)
The phosphor layer 7 is a layer having a wavelength conversion function of emitting light of different wavelengths by irradiation of excitation light, and includes at least one or more types of phosphors (not shown).

  Among phosphors, nano-sized semiconductors called quantum dots are preferable because high wavelength conversion efficiency can be obtained and the luminance and color reproducibility as a display are excellent. As a quantum dot, what the core as a light emission part was coat | covered with the shell as a protective film is mentioned. Examples of the core include cadmium selenide (CdSe) and the like, and examples of the shell include zinc sulfide (ZnS) and the like. By covering surface defects of CdSe particles with ZnS having a large band gap, quantum efficiency is improved. The phosphor may also be one in which the core is doubly covered by the first shell and the second shell. In this case, CdSe can be used for the core, zinc selenide (ZnSe) for the first shell, and ZnS for the second shell. The said fluorescent substance is used combining two or more types. In addition, a phosphor layer containing only one type of phosphor and a phosphor layer containing only another type of phosphor may be laminated.

  The phosphor is dispersed in a sealing resin for sealing. The sealing resin is, for example, a curable (UV) curable resin having an ethylenic double bond, an epoxy-based cationic photopolymerizable resin, an epoxy-amine-based thermosetting resin, a urethane-based thermosetting resin, etc. It can be formed using a resin.

  Among the above-mentioned curable resins, UV curable resins having an ethylenic double bond are widely used in terms of environmental consideration and low energy, and among them, polyfunctional (meth) acrylate resins are often used. However, the UV curing reaction of the polyfunctional (meth) acrylate resin alone has a slow reaction rate and is likely to cause cross-link density heterogeneity. Therefore, for the purpose of solving these, it is low with polyfunctional ethylenic double bonds. Molecular crosslinkers (hardeners) may be used. Although there are various types of the above-mentioned crosslinking agents, isocyanurate type compounds are sometimes used from the viewpoint of reactivity, weather resistance, crosslink density improvement, heat resistance and mechanical properties. In the case of the epoxy-based photocationic polymerizable resin, for the same reason as above, the epoxy-based resin may be cured using an isocyanurate type compound having a multifunctional epoxy group. In the epoxy-amine thermosetting resin, for the same reason as above, an amine resin may be cured using an isocyanurate type compound having a multifunctional epoxy group. A sealing resin using a urethane curing thermosetting resin can be obtained by thermosetting a resin having a polyfunctional hydroxyl group with a polyfunctional isocyanate. Here, there are various polyfunctional isocyanates, and isocyanurate type, biuret type, adduct type, or bifunctional type can be used, but in the same manner as above, isocyanurate having a polyfunctional isocyanate group Type compounds are often used. When the above-mentioned isocyanurate type compound is used as a curing agent when forming the phosphor layer 7, the affinity with the isocyanurate type compound used when forming the primer layer 5 is improved, and the phosphor layer 7 is formed. The adhesion between the above and the primer layer 5 is further improved.

  The phosphor layer 7 is formed by applying a mixed solution containing a phosphor, a curable resin, a curing agent as needed, and a solvent as needed on the primer layer 5 of the barrier film to form a coating film, as required Accordingly, another barrier film, which is separately prepared, may be laminated such that the primer layer 5 faces the phosphor layer 7, and the coating film may be cured.

  Curing of the coating film can be appropriately performed depending on the curable resin to be used. For example, when the curable resin is a thermosetting resin, it can be cured by heating or aging. On the other hand, when the curable resin is a photocurable resin, the coating film can be cured by curing (UV curing) the photocurable resin by irradiation of ultraviolet light. The photocurable resin may be further thermally cured after UV curing. By curing the curable resin, the sealing resin of the phosphor layer 7 is formed.

  The wavelength conversion sheet of the present embodiment described above can be used, for example, in a backlight unit. The backlight unit includes, for example, a light source, a light guide plate, a reflector, and the wavelength conversion sheet of the present embodiment. In the backlight unit, the light guide plate and the reflection plate are disposed in this order on one surface of the wavelength conversion sheet, and the light source is disposed on the side of the light guide plate (the surface direction of the light guide plate). For example, a blue light emitting diode element or the like is used as the light source.

[Method of producing barrier film and wavelength conversion sheet]
Next, an embodiment of a method for producing a barrier film and a wavelength conversion sheet of the present invention will be described. The method for producing a barrier film of the present embodiment is a method for producing a barrier film including a gas barrier film and a primer layer disposed on one outermost surface, and the composition for forming a primer layer of the present embodiment described above And obtaining the composition for forming a primer layer by the method for manufacturing a product, and applying the composition for forming a primer layer on the gas barrier film and curing the composition to form the primer layer. Further, according to the method for producing a wavelength conversion sheet of the present embodiment, a phosphor layer containing a cured product of a phosphor and a curable resin (sealing resin), and at least one surface of the phosphor layer are laminated. It is a manufacturing method of a wavelength conversion sheet provided with the barrier film which has a primer layer in the outermost surface by the side of the above-mentioned fluorescent substance layer, and the above-mentioned barrier film is obtained by the manufacturing method of the barrier film of this embodiment mentioned above, A step of applying a composition for forming a phosphor layer containing a phosphor and a curable resin on the primer layer of the barrier film to form a coated film, and curing the curable resin in the coated film Forming a phosphor layer. In the present embodiment, the surface of the gas barrier film forming the primer layer is the first substrate 11 in the barrier films 100, 300, 500 shown in FIG. 1, FIG. 3 and FIG. The barrier films 200 and 400 shown in FIG.

  When manufacturing the barrier film 100 shown in FIG. 1 and the wavelength conversion sheet 600 shown in FIG. 6 using it, it can manufacture, for example in the following procedures. In addition, the formation method of each layer is as having mentioned above. First, the first film 1 and the second film 2 are produced respectively. That is, the anchor coat layer 12 is formed on the first base material 11, and the inorganic thin film layer 13 and the gas barrier coating layer 14 are sequentially formed on the anchor coat layer 12 to produce the first film 1. The second film 2 can be produced similarly.

  An adhesive or a pressure-sensitive adhesive is applied on the gas barrier covering layer 14 of the first film 1 obtained, and is bonded to the surface of the second film 2 on the gas barrier covering layer 24 side for aging. A laminated film in which the film 1 of 1 and the second film 2 are bonded via the adhesive layer 4 is obtained. Bonding can be performed using a general laminating apparatus. The adhesive or pressure sensitive adhesive may be applied on the gas barrier coating layer 24 of the second film 2.

  The composition for forming a primer layer of the present embodiment described above is applied onto the first substrate 11 of the obtained laminated film and cured to form the primer layer 5. Further, the mat layer 6 is formed on the second base 21 of the laminated film. The formation order of the primer layer 5 and the mat layer 6 is not particularly limited. In addition, the mat layer 6 may be formed on the second base 21 of the second film 2 in advance before the first film 1 and the second film 2 are attached to each other. Furthermore, the primer layer 5 may be formed on the first base 11 of the first film 1 in advance before the first film 1 and the second film 2 are bonded to each other. Thereby, the barrier film 100 is obtained. Two barrier films 100 are produced.

  Next, on the primer layer 5 of one barrier film 100, a mixed solution containing a phosphor, a curable resin, a curing agent as needed, and a solvent as needed is applied to form a coating film, The primer layer 5 side of the other barrier film 100 is bonded on top, and the coating is cured to form a phosphor layer 7. By the above method, it is possible to obtain the wavelength conversion sheet 600 of the present embodiment having excellent gas barrier properties and excellent adhesion between the barrier film 100 and the phosphor layer 7.

  The preferred embodiment of the present invention has been described above in detail, but the technical scope of the present invention is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention. It is.

  For example, in the barrier film shown in FIGS. 1 to 5, the mat layer 6 and the anchor coat layers 12 and 22 may not be provided.

  In the barrier films 100, 200, 500 shown in FIG. 1, FIG. 2, FIG. 5 and FIG. 6, in the barrier layers 15, 25, multiple inorganic thin film layers 13, 23 and gas barrier coating layers 14, 24 are alternately laminated. It may be done. Moreover, in the barrier films 300 and 400 shown in FIG. 3 and FIG. 4, the barrier layers 15 and 25 are obtained by laminating the inorganic thin film layers 13 and 23 and the gas barrier coating layers 14 and 24 one by one. It is also good.

  In the barrier film shown in FIGS. 1 to 5, the orientations of the first film 1 and the second film 2 are not limited to the orientations shown in the drawings, and may be arranged in the opposite direction.

  The barrier film may further include one or more films having the same configuration as the first film and the second film, in addition to the first film and the second film.

  In the wavelength conversion sheet shown in FIG. 6, the pair of barrier films sandwiching the phosphor layer 7 may have different configurations. Moreover, the mat layer 6 may not necessarily be provided on both sides of the wavelength conversion sheet, and may be provided only on one surface.

  Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.

  In the following Examples and Comparative Examples, room temperature means 25 ° C. Moreover, in the following Examples and Comparative Examples, the components used for the primer layer and the phosphor layer are collectively shown in Table 1.

Example 1
(Preparation of composition for forming primer layer)
After adding 200 parts by mass of a solvent (ethyl acetate) to 100 parts by mass of acrylic polyol (manufactured by DIC, trade name: Acridic A-801-P) and stirring, an isocyanate based silane coupling agent (Shin-Etsu Chemical Co., Ltd. stock) Company-made, brand name: KBE-9007) 12.5 mass parts It added at room temperature and stirred for 24 hours. Next, 10 parts by mass of a methacrylic silane coupling agent (Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) was added, and the mixture was stirred at room temperature for 24 hours. Thereafter, 10 parts by mass of isocyanurate type hexamethylene diisocyanate (manufactured by Asahi Kasei Corporation, trade name: DURANATE TPA 100) as a curing agent was added, and the mixture was stirred at room temperature for 1 hour to obtain a composition for forming a primer layer.

(Preparation of barrier film)
A polyester resin solution is applied by a bar coat method on a corona-discharge-treated side of a biaxially stretched polyethylene terephthalate film (trade name: P60, thickness: 16 μm, Toray Industries, Inc.), one side of which is subjected to corona discharge treatment. By drying and curing at 80 ° C. for 1 minute, a 100 nm thick anchor coat layer was formed.

A silicon oxide material (made by Canon Optron Co., Ltd.) is evaporated by electron beam heating under a pressure of 1.5 × 10 ^-2 Pa using an electron beam heating type vacuum deposition apparatus to form an inorganic thin film on the above anchor coat layer. An 80 nm thick SiOx film was formed as a layer. In addition, the acceleration voltage in vapor deposition was 40 kV, and the emission current was 0.2A. A coating solution in which a hydrolyzate of tetraethoxysilane (containing a siloxane bond) and polyvinyl alcohol are mixed at a mass ratio of 1: 1 is applied on the SiOx film by a bar coating method, and dried and cured at 120 ° C. for 1 minute. A gas barrier coating layer 400 nm thick was formed. Then, an 80 nm-thick SiOx film was formed as an inorganic thin film layer on the gas barrier coating layer in the same manner as described above. Furthermore, a gas barrier coating layer having a thickness of 400 nm was formed on the SiOx film in the same manner as described above. Thus, a first film was obtained. The water vapor transmission rate of the first film was 0.5 g / (m ² · day).

An adhesive (main agent: Takelac A525, curing agent: Takenate A50, manufactured by Mitsui Chemicals, Inc.) is coated on the gas barrier coating layer of the first film to form an adhesive layer, and biaxially oriented polyethylene as a second film A corona discharge-treated surface of a terephthalate film (trade name: FE 2001, thickness: 25 μm, manufactured by FUTAMURA CHEMICAL CO., LTD., Water vapor transmission rate 25 g / (m ² · day)) is bonded and aged at 40 ° C. for 2 days did. Thus, a laminated film (1) in which the first film and the second film were bonded via the adhesive layer was obtained. The thickness of the adhesive layer was 4 μm.

  The composition for forming a primer layer is coated with a wire bar coater on the polyethylene terephthalate film (first base material) of the first film in the obtained laminated film (1) to form a coated film, 100 The primer layer was formed by drying at 60 ° C. for 60 seconds to cure the coating. The thickness of the primer layer was 1 μm.

  In addition, 100 parts by mass of an acrylic polyol resin (manufactured by DIC, trade name: Acrydic A-814), and an isocyanate-based curing agent (manufactured by DIC) on the polyethylene terephthalate film (second base) of the second film Brand name: Burnoc DN-980, hexamethylene diisocyanate compound) 8.5 parts by mass, fine particles (polyurethane, average particle diameter 2 μm) 10 parts by mass, solvent (ethyl acetate) 70 parts by mass A composition for forming a mat layer And dried by heating to cure to form a 3 μm thick mat layer. Thereby, the barrier film which has a structure shown in FIG. 3 was obtained. Two sheets of this barrier film were prepared.

(Preparation of wavelength conversion sheet)
On the primer layer of one of the barrier films, the core is cadmium selenide (CdSe), the shell is zinc sulfide (ZnS), a quantum dot light emitter with a particle diameter of 6 nm, and an acrylic having an acryloyl group at the end of the main chain or side chain A composition for forming a phosphor layer is coated and coated with a photocurable resin based on an aliphatic group and an aliphatic isocyanurate type curing agent having an allyl group (Nippon Kasei Co., Ltd., trade name: Tyck triallylisocyanurate) And the other barrier film primer layer was attached thereto. The coating film was exposed to light at an exposure dose of 2100 mJ / cm ² using an ultraviolet irradiation device and cured to form a phosphor layer (100 μm in thickness) having a wavelength conversion function. Thus, a wavelength conversion sheet was obtained.

Example 2
(Preparation of composition for forming primer layer)
GMA (Mitsubishi Gas Chemical Co., Ltd.) after adding 200 parts by mass of a solvent (ethyl acetate) to 100 parts by mass of a carboxyl group-containing polyester resin (Toyobo Co., Ltd., trade name: Byron 240, hydroxyl value 9 mg KOH / g) 10 parts by mass of glycidyl methacrylate, manufactured by Company, was added and stirred at 40 ° C. for 24 hours. Next, 10 parts by mass of aliphatic isocyanurate type curing agent having an allyl group (manufactured by Nippon Kasei Co., Ltd., trade name: Tyck triallyl isocyanurate), and a photopolymerization initiator (manufactured by BASF, trade name: IRAGACURE 184) 1 part by mass was added and stirred at room temperature for 1 hour to obtain a composition for forming a primer layer.

(Preparation of barrier film and wavelength conversion sheet)
In the same manner as Example 1, a laminated film (1) was produced. The composition for forming a primer layer was coated with a wire bar coater on the first substrate in the obtained laminated film (1) to form a coating, and the coating was dried at 100 ° C. for 60 seconds. Then, the primer layer was formed by exposing and hardening the said coating film by the exposure amount of 1000 mJ / cm < ² > using an ultraviolet irradiation device. The thickness of the primer layer was 1 μm. Further, in the same manner as in Example 1, a mat layer was formed on the second base material to obtain a barrier film. Furthermore, a wavelength conversion sheet was obtained in the same manner as in Example 1 except that the above barrier film was used.

[Example 3]
(Preparation of composition for forming primer layer)
After adding 200 parts by mass of a solvent (ethyl acetate) to 100 parts by mass of acrylic polyol (manufactured by DIC, trade name: Acridic A-801-P) and stirring, an isocyanate based silane coupling agent (Shin-Etsu Chemical Co., Ltd. stock) 6 mass parts of company make and brand name: KBE-9007) were added, and it stirred at room temperature for 24 hours. Thereafter, 10 parts by mass of an aliphatic isocyanurate type curing agent having an alkoxysilyl group (Shin-Etsu Chemical Co., Ltd., trade name: KBM-9659, tris- (trimethoxysilylpropyl) isocyanurate) is added, and the mixture is allowed to stand for 1 hour at room temperature. The mixture was stirred to obtain a composition for forming a primer layer.

(Preparation of barrier film and wavelength conversion sheet)
A barrier film and a wavelength conversion sheet were obtained in the same manner as in Example 1 except that the composition for forming a primer layer was used. In this example, the hydroxyl group which is the functional group A in the primer layer has an intermolecular bonding property to, for example, -COO- group of the curable resin used in the phosphor layer.

Example 4
(Preparation of composition for forming primer layer)
GMA (Mitsubishi Gas Chemical Co., Ltd.) after adding 200 parts by mass of a solvent (ethyl acetate) to 100 parts by mass of a carboxyl group-containing polyester resin (Toyobo Co., Ltd., trade name: Byron 240, hydroxyl value 9 mg KOH / g) 5 parts by mass of glycidyl methacrylate, manufactured by Company, was added, and the mixture was stirred at 40 ° C. for 24 hours. Then, an aliphatic isocyanurate type curing agent having an epoxy group (Nissan Chemical Industries, Ltd., trade name: TEPIC-VL 10 parts by mass, and a photopolymerization initiator (Wako Pure Chemical Industries, Ltd., trade name: WPI- 116) 1 mass part was added and it stirred at room temperature for 1 hour, and obtained the composition for primer layer formation.

(Preparation of barrier film and wavelength conversion sheet)
A barrier film and a wavelength conversion sheet were obtained in the same manner as in Example 1 except that the composition for forming a primer layer was used.

[Example 5]
(Preparation of composition for forming primer layer)
GMA (Mitsubishi Gas Chemical Co., Ltd.) after adding 200 parts by mass of a solvent (ethyl acetate) to 100 parts by mass of a carboxyl group-containing polyester resin (Toyobo Co., Ltd., trade name: Byron 240, hydroxyl value 9 mg KOH / g) 5 parts by mass of glycidyl methacrylate, manufactured by Company, was added, and the mixture was stirred at 40 ° C. for 24 hours. Next, 10 parts by mass of aliphatic isocyanurate type curing agent having an allyl group (manufactured by Nippon Kasei Co., Ltd., trade name: Tyck triallyl isocyanurate), and a photopolymerization initiator (manufactured by BASF, trade name: IRAGACURE 184) 1 part by mass was added and stirred at room temperature for 1 hour to obtain a composition for forming a primer layer.

(Preparation of barrier film and wavelength conversion sheet)
A barrier film was obtained in the same manner as in Example 1 except that the composition for forming a primer layer was used. On the primer layer of one barrier film, the core is cadmium selenide (CdSe), the shell is zinc sulfide (ZnS), the quantum dot light emitter having a particle diameter of 6 nm, and the amine having an amino group at the end of the main chain or side chain A coating film is formed by applying a composition for forming a phosphor layer containing a thermosetting thermosetting resin and an aliphatic isocyanurate type curing agent having an epoxy group (manufactured by Nissan Chemical Industries, Ltd., trade name: TEPIC-VL). It formed and the primer layer of the other barrier film was bonded together there. The above-mentioned coating film was heated at 100 ° C. for 2 minutes in an oven for curing to form a phosphor layer (100 μm in thickness) having a wavelength conversion function. Thus, a wavelength conversion sheet was obtained.

[Example 6]
(Preparation of composition for forming primer layer)
200 parts by mass of solvent (ethyl acetate) is added to 100 parts by mass of aminoethylated acrylic resin (Nippon Shokuhin Co., Ltd., trade name: POLYMENT NK-350, amine value 0.6 to 1.0 mmol / g-solid) After stirring, 5 parts by mass of GMA (glycidyl methacrylate, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature for 24 hours. Next, 10 parts by mass of an aliphatic isocyanurate type curing agent having an epoxy group (manufactured by Nissan Chemical Industries, Ltd., trade name: TEPIC-VL), and a photopolymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 1 part by weight of WPI-116 was added, and the mixture was stirred at room temperature for 1 hour to obtain a composition for forming a primer layer.

(Preparation of barrier film and wavelength conversion sheet)
A barrier film and a wavelength conversion sheet were obtained in the same manner as in Example 1 except that the composition for forming a primer layer was used.

[Example 7]
(Preparation of composition for forming primer layer)
200 parts by mass of solvent (ethyl acetate) is added to 100 parts by mass of aminoethylated acrylic resin (Nippon Shokuhin Co., Ltd., trade name: POLYMENT NK-350, amine value 0.6 to 1.0 mmol / g-solid) After stirring, 5 parts by mass of GMA (glycidyl methacrylate, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature for 24 hours. Next, 10 parts by mass of aliphatic isocyanurate type curing agent having an allyl group (manufactured by Nippon Kasei Co., Ltd., trade name: Tyck triallyl isocyanurate), and a photopolymerization initiator (manufactured by BASF, trade name: IRAGACURE 184) 1 part by mass was added and stirred at room temperature for 1 hour to obtain a composition for forming a primer layer.

(Preparation of barrier film and wavelength conversion sheet)
A barrier film was obtained in the same manner as in Example 1 except that the composition for forming a primer layer was used. A wavelength conversion sheet was obtained in the same manner as in Example 5 except that the barrier film was used.

[Example 8]
(Preparation of composition for forming primer layer and preparation of barrier file)
In the same manner as in Example 7, a composition for forming a primer layer and a barrier file were obtained.

(Preparation of wavelength conversion sheet)
On the primer layer of one of the barrier films, the core is cadmium selenide (CdSe), the shell is zinc sulfide (ZnS), a quantum dot light emitter with a particle diameter of 6 nm, and an epoxy having an epoxy group at the end of the main chain or side chain Is coated with a composition for forming a phosphor layer containing an epoxy-based photocurable resin and an aliphatic isocyanurate type curing agent having an epoxy group (Nissan Chemical Industry Co., Ltd., trade name: TEPIC-VL) It formed and the primer layer of the other barrier film was bonded together there. The coating film was exposed to light at an exposure of 1000 mJ / cm ² using an ultraviolet irradiation apparatus and cured to form a phosphor layer (100 μm in thickness) having a wavelength conversion function. Thus, a wavelength conversion sheet was obtained.

[Example 9]
(Preparation of composition for forming primer layer)
In a nitrogen atmosphere, 0.1 parts by mass of AIBN (2,2'-azobis (isobutyro nitrile), manufactured by Wako Pure Chemical Industries, Ltd.) to 100 parts by mass of GMA (manufactured by Mitsubishi Gas Chemical Co., Ltd., glycidyl methacrylate) Was added and stirred to polymerize. The product was dissolved in 200 parts by mass of a solvent (ethyl acetate), 5 parts by mass of MAA (Mitsubishi Gas Chemical Co., Ltd., methacrylic acid) was added, and the mixture was stirred at 40 ° C. for 24 hours. Thereafter, 10 parts by mass of an aliphatic isocyanurate type curing agent having an allyl group (manufactured by Nippon Kasei Co., Ltd., trade name: Taiko triallyl isocyanurate), and a photopolymerization initiator (manufactured by BASF, trade name: IRAGACURE 184) 1 part by mass was added and stirred at room temperature for 1 hour to obtain a composition for forming a primer layer.

(Preparation of barrier film and wavelength conversion sheet)
A barrier film and a wavelength conversion sheet were obtained in the same manner as in Example 5 except that the composition for forming a primer layer was used.

[Example 10]
(Preparation of composition for forming primer layer, and preparation of barrier film and wavelength conversion sheet)
Composition for forming a primer layer in the same manner as in Example 1 except that the curing agent used for the composition for forming a primer layer was changed to an aromatic isocyanurate type curing agent (made by Tosoh Corp., trade name: Coronate 2030) An object, a barrier film and a wavelength conversion sheet were obtained.

[Example 11]
(Preparation of composition for forming primer layer and preparation of barrier film)
In the same manner as Example 1, a composition for forming a primer layer and a barrier film were obtained.

(Preparation of wavelength conversion sheet)
The core is cadmium selenide (CdSe), the shell is zinc sulfide (ZnS), the quantum dot light emitter has a particle diameter of 6 nm, and the polyol has a hydroxyl group at the main chain or side chain on the primer layer of one barrier film. A composition for forming a phosphor layer comprising a thermosetting resin and isocyanurate type hexamethylene diisocyanate (trade name: DURANATE TPA 100, manufactured by Asahi Kasei Corporation) as a curing agent is applied to form a coating film, and The other barrier film primer layer was laminated. The above-mentioned coating film was heated at 100 ° C. for 2 minutes in an oven for curing to form a phosphor layer (100 μm in thickness) having a wavelength conversion function. Thus, a wavelength conversion sheet was obtained.

Comparative Example 1
(Preparation of composition for forming primer layer, and preparation of barrier film and wavelength conversion sheet)
Composition for forming a primer layer in the same manner as in Example 1 except that the curing agent used for the composition for forming a primer layer was changed to biuret-type hexamethylene diisocyanate (trade name: DURANATE 24A-100, manufactured by Asahi Kasei Co., Ltd.) An object, a barrier film and a wavelength conversion sheet were obtained.

Comparative Example 2
(Preparation of composition for forming primer layer, and preparation of barrier film and wavelength conversion sheet)
Composition for forming a primer layer in the same manner as in Example 1 except that the curing agent used for the composition for forming a primer layer was changed to adduct type hexamethylene diisocyanate (trade name: DURANATE P301-75E, manufactured by Asahi Kasei Co., Ltd.) A barrier film and a wavelength conversion sheet were obtained.

<Evaluation of adhesion>
The wavelength conversion sheets obtained in Examples and Comparative Examples were cut into strips of 1 cm in width, and the cut wavelength conversion sheets were fixed on a glass plate. The primer layer of the fixed strip-like wavelength conversion sheet is peeled off from the phosphor layer at a speed of 300 mm / min in a direction perpendicular to the glass plate using a TENSILON universal material tester (manufactured by A & D Co.) And the strength required for peeling was measured. The adhesion was determined to be "o" when the peel strength is 3 N / 1 cm or more, and "x" when the peel strength is less than 3 N / 1 cm. The case where this judgment is "o" was taken as pass. The results are shown in Table 1.

<Evaluation of color change>
The barrier films prepared in Examples and Comparative Examples were irradiated with ultraviolet light of wavelength 300 to 400 nm at an irradiance of 60 W / m ² for 1000 hours using a xenon weather meter, and the yellow index (YI of the barrier film before and after irradiation) ) (ΔYI) was determined. The yellow index was measured using Color Cute i (trade name) manufactured by Suga Test Instruments Co., Ltd. The color change was determined as “〇” when ΔYI was less than 2.0, “Δ” when it was 2.0 or more and less than 3.0, and “x” when it was 3.0 or more. The case where this determination is “o” or “Δ” was taken as pass. The results are shown in Table 1.

<Measurement of water vapor permeability>
The water vapor transmission rate of the barrier film prepared in the examples and comparative examples was measured by the infrared sensor method according to JIS K 7129 using a water vapor transmission rate measuring device (manufactured by MOCON, trade name: Permatran) and the temperature of the transmission cell was 40 The relative humidity of the high humidity chamber was 90% RH, and the relative humidity of the low humidity chamber was 0% RH. The results are shown in Table 1.

  As apparent from the results shown in Table 1, adhesion to the phosphor layer is obtained by using a specific polyfunctional compound in the composition for forming a primer layer and using an isocyanurate type compound as a curing agent. It was confirmed that an excellent primer layer could be formed. Moreover, it was confirmed by using an aliphatic isocyanurate type compound as a hardening | curing agent that the primer layer which can suppress the color change after time-lapse can be formed, having favorable adhesiveness with respect to a fluorescent substance layer.

DESCRIPTION OF SYMBOLS 1 ... 1st film, 2 ... 2nd film, 3 ... 3rd film, 4 ... Adhesive layer, 5 ... Primer layer, 6 ... Matt layer, 7 ... Phosphor layer, 11 ... 1st base material, 21 ... 2nd base material, 31 ... 3rd base material, 12, 22 ... anchor coat layer, 13, 23 ... inorganic thin film layer, 14, 24 ... gas barrier coating layer, 15, 25 ... barrier layer, 100, 200, 300, 400, 500 ... barrier film, 600 ... wavelength conversion sheet.

Claims (6)

A composition for forming a primer layer for forming a primer layer adjacent to a phosphor layer of an optical laminate, comprising:
Containing multifunctional compound and curing agent,
The multifunctional compound has a functional group A having reactivity or intermolecular bondability with the curable resin used in the phosphor layer at the end of the main chain or side chain of the resin skeleton, and the functional group A functional group B which is the same as or different from A and has reactivity to the curing agent,
The functional group B includes at least one functional group selected from the group consisting of a hydroxyl group, a vinyl group, an acryloyl group, a methacryloyl group, a silanol group, an amino group and a carboxyl group,
The composition for forming a primer layer, wherein the curing agent comprises an isocyanurate type compound.   The composition for primer layer formation of Claim 1 whose said isocyanurate type compound is an aliphatic isocyanurate type compound.   The composition for primer layer formation of Claim 1 or 2 whose said functional group A and the said functional group B are different functional groups. A gas barrier film,
The primer layer which consists of hardened | cured material of the composition for primer layer formation as described in any one of Claims 1-3 arrange | positioned at one outermost surface,
Barrier film. A phosphor layer comprising a cured product of a phosphor and a curable resin, and the barrier film according to claim 4 laminated on at least one surface of the phosphor layer,
The said barrier film is a wavelength conversion sheet provided with the said primer layer in the outermost surface at the side of the said fluorescent substance layer. The said primer layer of a barrier film provided with a gas-barrier film and the primer layer which consists of hardened | cured material of the composition for primer layer formation as described in any one of Claims 1-3 arrange | positioned at one outermost surface. Coating a composition for forming a phosphor layer containing a phosphor and a curable resin thereon to form a coating film;
Curing the curable resin in the coating to form a phosphor layer;
The manufacturing method of the wavelength conversion sheet which has.

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