TW201940611A - Functional member - Google Patents

Abstract

The purpose of this invention is to improve adhesion between a substrate 10 and a highly adhesive layer 20 and adhesion between the highly adhesive layer 20 and a functional layer 30, and maintain adequate adhesion after long-term exposure to harsh environments such as high-temperature, high-humidity environments. In order to achieve this purpose, this functional member is obtained by laminating, on at least one side of the substrate 10, the highly adhesive layer 20 and the functional layer 30, in this order, wherein the composition for forming the highly adhesive layer 20 contains a polyester-acrylic composite resin having a glycidyl group, and the solid acid value of said composition falls within the range of 2.5 to 6.0 mgKOH/g, inclusive. The composition for forming the functional layer 30 contains a compound having a functional group which is reactive to the glycidyl group, and the solid acid value of said composition does not exceed 4.0 mgKOH/g.

Description

Functional building block

The present invention relates to functional members, films, sheets, etc. that are laminated in order according to a substrate, an easy-to-adhesive layer, and a functional layer. More specifically, the present invention relates to maintaining even in a severe environment such as high temperature and high humidity. Functional members, films, and sheets with sufficient adhesion.

Plastic materials are widely used as materials for electronic devices because of their light weight, processing suitability, and productivity. Plastic materials may be used as a single unit, but in many cases, a function layer having a specific function in the surface area layer is added to the function depending on the application. In particular, in recent years, plastic materials have been used in areas that have not been used in place of glass or metal materials. With this, plastic materials are also required to have high interlayer stability in severe environments such as high temperatures and high humidity.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 09-176518
[Patent Document 2] International Publication No. 2015/170560

[Problems to be Solved by the Invention]

However, thermoplastic resins such as polyester, polyamide, polystyrene, polyolefin, polycarbonate, and polyimide, which are raw materials for plastic materials, are usually melted to form fibers, films, and sheets, but the surface is crystallized. In many cases, the adhesiveness of inks and adhesives is lacking. Among them, the thin film has a highly crystalline alignment through the steps of stretching and heat fixing, so the level of adhesion is very low, and it is known that the adhesion is generally poor.

The use of materials with high affinity with plastic films for the functional layer can solve this situation, but the materials of the functional layer are extremely limited, and the necessary functions are sometimes damaged. Therefore, as in Patent Document 1 or Patent Document 2, the adhesion between the substrate and the easily-adhesive layer and the adhesion of the easily-adhesive layer are improved by providing an easily-adhesive layer with high affinity between the substrate and the functional layer. The method of adhesion of the functional layer. However, although the functional plastic film provided with an easy-to-adhesive layer has good initial adhesion, the adhesiveness between the substrate and the easy-to-adhesive layer and The adhesiveness between the easy-adhesion layer and the functional layer is reduced, and a problem such as peeling of the easy-adhesion layer and / or the functional layer occurs.

As mentioned above, in areas that have not been used in recent years, such as transparent conductive substrates for touch panels, flexible circuit boards, substrates for flexible displays, substrates for organic EL, substrates for LED lighting, etc. The materials of electronic devices also use plastic materials, and require high initial adhesion and stability over time under severe environments such as high temperature and high humidity, which were not previously required.

The object of the present invention is to improve the adhesion between the substrate and the easy-adhesive layer and the adhesion between the easy-adhesive layer and the functional layer, and to maintain sufficient adhesion even if exposed to a severe environment such as high temperature and humidity for a long time. Sex.

[Means to solve the problem]

The functional member of the present invention is a functional member laminated on at least one side of a substrate in the order of an easy-adhesive layer and a functional layer, and is characterized in that the composition for forming the easy-adhesive layer includes a polymer having a glycidyl group. Ester-acrylic composite resin, and the solid component of the composition has an acid value of 2.5 to 6.0 mgKOH / g, and the composition for forming the aforementioned functional layer includes a compound having a functional group reactive with a glycidyl group, and the composition The solid content acid value is 4.0 mgKOH / g or less.

In the functional member of the present invention, it is preferable that the composition for forming the easy-adhesion layer is a composition containing the polyester-acrylic composite resin as a main component.

In the functional member of the present invention, it is preferable that the content of the acrylic resin component in all the constituent components of the entire solid component forming the composition for the easy-adhesion layer is 20 to 50% by weight.

In the functional member of the present invention, the functional group having reactivity with the glycidyl group is preferably a hydroxyl group.

In the functional member of the present invention, it is preferred that the surface of the base material laminated with the easily-adhesive layer is a surface-treated functional group having a reactive group with a glycidyl group.

In the functional member of the present invention, it is preferable that the functional group having a reactivity with a glycidyl group introduced by the surface treatment is a hydroxyl group.

[Inventive effect]

According to the present invention, the adhesiveness between the base material and the easy-adhesive layer of the functional member and the adhesiveness between the easy-adhesive layer and the functional layer can be improved. In particular, even in a severe environment such as high temperature and high humidity, there is little change in the adhesion of the functional member, and good adhesion can be maintained.

Hereinafter, embodiments of the functional member of the present invention will be described with reference to FIGS. 1 and 2.

The basic structure of the functional member of the present invention is shown in FIG. 1, and includes a base material 10, an easy-adhesion layer 20, and a functional layer 30. The functional member may be provided with a back surface coating layer 40 (see FIG. 2) on the surface opposite to the surface of the laminated organic energy layer 30 as shown in FIG. 1.

First, the base material 10 is demonstrated. The substrate 10 is suitable for using a plastic film. As the plastic film, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, and triethylfluorene-based fiber can be used. The substrate can be selected according to applications such as transparency, heat resistance, mechanical strength, dimensional stability, color tone, and the like, such as pigment, polymethyl methacrylate, polyvinyl chloride, polynorbornene, and polyimide compounds. Among them, the polyethylene terephthalate film, which is stretched, especially biaxially stretched, is suitable for use because it has excellent mechanical strength and dimensional stability.

The thickness of the substrate 10 is not particularly limited, and the materials used can be appropriately selected. In consideration of operability, it is generally 1 μm or more and 300 μm or less, and preferably 23 μm or more and 188 μm or less.

In some cases, the substrate 10 may be subjected to a surface treatment such as a plasma treatment, a corona discharge treatment, or a far-ultraviolet irradiation treatment. By applying these surface treatments, the wettability of the easy-adhesion layer 20 to the substrate 10 is improved, and the adhesion can be improved. In particular, when the functional group introduced by the plasma treatment or the corona discharge treatment is a functional group reactive with glycidyl group, an addition reaction with the glycidyl group easily adhered to the layer 20 described later is generated, and the adhesion is further improved. .

Here, the functional group having reactivity with a glycidyl group introduced by the aforementioned surface treatment includes, for example, a hydroxyl group, a carboxyl group, a hydroperoxy group, a carbonyl group, and an epoxy group, and a hydroxyl group is preferred.

Next, the easy adhesion layer 20 will be described. The composition for forming the easy-adhesion layer 20 is not particularly limited as long as it is a composition containing a polyester-acrylic composite resin having a glycidyl group and a specific solid component acid value, and the ionizing radiation curable resin can be used. Compounds such as thermosetting resins, thermoplastic resins, etc. can be used alone or in combination of 2 or more, and can be used separately according to the purpose.

Although the adhesion mechanism is not clear, the composition for forming the easy-adhesion layer 20 is a polyester-acrylic composite resin having a specific solid component acid value and having a glycidyl group. In addition, it is used for forming a functional layer 30 described later. The composition has a specific solid component acid value, and because it contains a compound having a functional group reactive with glycidyl group, an addition reaction occurs between the easy-adhesion layer 20 and the functional layer 30, thereby improving the easy-adhesion layer 20 and Adhesion of the functional layer 30.
In addition, the adhesiveness with the base material 10 differs depending on the material of the base material 10, but when the adhesiveness is insufficient, the base material 10 can be improved by applying the surface treatment described above.
In addition, when the polar group introduced into the base material 10 by the surface treatment is a specific functional group as described above, an addition reaction occurs between the base material 10 and the easy-adhesion layer 20 to further improve adhesion.

The solid component acid value of the composition for forming the easily-adhesive layer 20 is preferably 2.5 mgKOH / in order to improve the adhesion between the substrate 10 and the easily-adhesive layer 20 and the adhesion between the easily-adhesive layer 20 and the functional layer 30. g or more, more preferably 3.0 mgKOH / g or more, more preferably 6.0 mgKOH / g or less, and still more preferably 4.5 mgKOH / g or less. When the acid value is less than 2.5 mgKOH / g, the addition reaction between the functional group having reactivity with the glycidyl group and the glycidyl group does not sufficiently proceed, so the adhesion and easy adhesion between the substrate 10 and the easy-adhesion layer 20 Then, the adhesion between the layer 20 and the functional layer 30 may be reduced. When it is greater than 6.0 mgKOH / g, side reactions such as the ring-opening polymerization of the glycidyl group are preferential, the addition reaction is hindered, and a substrate is generated. The unfavorable situation in which the adhesion between 10 and the easy-adhesion layer 20 and the adhesion between the easy-adhesion layer 20 and the functional layer 30 is reduced.
The solid content acid value in the present invention is a value calculated from the acid value obtained by the indicator titration method specified in JIS K 2501: 2003 and its solid content concentration.

The acid value of the composition for forming the easy-adhesion layer 20 can be adjusted by introducing a functional group such as a carboxyl group, a sulfonic acid group, a phosphate group, or a phenolic hydroxyl group into the compound constituting the composition.

The composition is preferably a polyester-acrylic composite resin as a main component. By using the polyester-acrylic composite resin as a main component, the adhesion between the substrate 10 and the easily-adhesive layer 20 and the adhesion between the easily-adhesive layer 20 and the functional layer 30 can be improved.
The main component of the present invention means that when the total solid content of the components constituting the composition is 100 parts by weight, the component thereof exceeds 50 parts by weight.

The polyester-acrylic composite resin may be either a mixture of a polyester resin and an acrylic resin, or a compound containing both a polyester component and an acrylic component as constituent components, or they may be composited. Examples of the compound containing both the polyester component and the acrylic component as constituent components include a polyester-acrylic copolymer. In consideration of storage stability of the composition, transparency or smoothness of the film, a compound containing both a polyester component and an acrylic component as constituent components is preferred.

The component ratio of the composition for forming the easy-adhesion layer 20 is not necessarily limited. When the content of the acrylic resin component in the entire solid component composition is within the range of 20 to 50% by weight, the substrate 10 and the substrate 10 are further increased. Adhesion of the easy-adhesion layer 20 and adhesion of the easy-adhesion layer 20 and the functional layer 30.

The content of the glycidyl group of the aforementioned polyester-acrylic composite resin is expressed in terms of the gram of the compound containing 1 gram equivalent of the epoxy group, that is, it can be expressed by epoxy equivalent.
The epoxy equivalent in the aforementioned polyester-acrylic composite resin is preferably 100 g / eq. Or more, and more preferably 120 g / eq. Or more, in order to improve the adhesion between the easy-adhesion layer 20 and the functional layer 30, and most preferably Above 150 g / eq., Below 100,000 g / eq., More preferably below 10,000 g / eq., Most preferably below 5000 g / eq. By satisfying this range, sufficient adhesion can be maintained even after long-term exposure in a severe environment such as initial adhesion and high temperature and high humidity.
When the epoxy equivalent is less than 100 g / eq., The rigidity or toughness of the easy-adhesion layer 20 is insufficient, and the adhesion between the base material 10 and the easy-adhesion layer 20 and / or the close adhesion of the easy-adhesion layer 20 and the functional layer 30 is caused. Sex decreased. When it exceeds 100,000 g / eq., The content of glycidyl group is too small, and the amount of chemical bonds formed between the substrate 10 and the easily-adhesive layer 20 and between the easily-adhesive layer 20 and the functional layer 30 by addition reaction. Inadequate, in a severe environment such as high temperature and high humidity, when exposed for a long period of time, a defect such as peeling may occur between the substrate 10 and the easy-adhesive layer 20 and / or between the easy-adhesive layer 20 and the functional layer 30.
The epoxy equivalent can be obtained by a method specified in JIS K 7236: 2009.

In addition, the easy-adhesion layer 20 may suitably contain an antistatic agent, an antioxidant, a flattening agent, an anti-blocking agent, a slip agent, a flame retardant, an ultraviolet absorber, a dispersant, and the like, as long as the function of the present invention is not hindered. Coagulants, pigments, dyes, lubricants and other additives.

The thickness of the easy-adhesion layer 20 is 0.01 μm or more and 50 μm or less, preferably 0.1 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 2 μm or less. By having such a thickness, the adhesion between the substrate 10 and the easy-adhesion layer 20 and the adhesion between the easy-adhesion layer 20 and the functional layer 30 can be improved, and even if exposed for a long time under severe environments such as high temperature and humidity It can also maintain sufficient adhesion.
The thickness of the easy-adhesion layer 20 can be measured by, for example, a reflection spectrometer (FE-300UV: Otsuka Electronics Co., Ltd.).

Next, the functional layer 30 will be described. The composition for forming the functional layer 30 is not particularly limited as long as it is a functional group that is reactive with glycidyl group and has a specific solid component acid value. Ionizing radiation hardening resin, thermosetting resin, Compounds such as thermoplastic resins may be used alone or in combination of two or more, and they may be used separately according to the purpose.

This ionizing radiation-curable resin can be cured by irradiating ionizing radiation (ultraviolet rays or electron beams) to one or more ionizing radiation-curable coating materials mixed with a photopolymerizable prepolymer or a photopolymerizable monomer. By. Here, a photopolymerizable prepolymer, for example, an acrylic prepolymer having one or more (meth) acrylfluorene groups in one molecule is particularly suitable for use. Examples of the acrylic prepolymer include urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate, polyperfluoroalkyl acrylate, polysiloxane acrylate, and the like.

In addition, a photopolymerizable monomer, such as an acrylic monomer having one or two (meth) acrylfluorenyl groups in one molecule, is particularly suitable for use. Examples include monofunctional acrylic monomers such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-butoxyethyl acrylate; for example, 1,6-hexane Difunctional acrylic monomers such as glycol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, etc .; for example Difunctional pentaerythritol hexaacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and other polyfunctional (more than trifunctional) acrylic monomers; etc. These photopolymerizable monomers can be used alone or in combination of two or more kinds. The blending ratio of the photopolymerizable prepolymer and the photopolymerizable monomer is not particularly limited, and can be appropriately set according to the purpose and application.

Examples of the thermosetting resin include polyester acrylate resins, polyurethane acrylate resins, epoxy acrylate resins, epoxy resins, melamine resins, phenol resins, and polysiloxanes. Department of resin and so on.

Examples of the thermoplastic resin include polyester resin, acrylic resin, polycarbonate resin, cellulose resin, acetal resin, vinyl resin, polyethylene resin, polystyrene resin, and polypropylene. Resins, polyamido resins, polyamido resins, fluorine resins, and the like.

The functional group contained in the composition for forming the functional layer 30 has functional groups that are reactive with the glycidyl group of the easy-adhesion layer 20, and is not particularly limited. For example, a hydroxyl group, an amino group, a carboxyl group, a carboxylic anhydride, an imidazole group, a mercapto group, and an isocyanate can be used Base etc.
When considering the ease of control of the reaction at the time of manufacture, a hydroxyl group is particularly preferable.

The solid component acid value of the composition for forming the functional layer 30 is preferably 4.0 mgKOH / g or less, and more preferably 3.0 mgKOH / g or less in order to improve the adhesion between the easy-adhesion layer 20 and the functional layer 30. When the acid value exceeds 4.0 mgKOH / g, side reactions such as ring-opening polymerization of the glycidyl group in the easily-adhesive layer 20 are preferred, and a disadvantage that the addition reaction exhibiting the aforementioned adhesion is hindered is caused.
The solid content acid value is determined by the same method as the solid content acid value of the composition for forming the easy-adhesion layer 20 described above.

The functional layer 30 may further be based on a hardening method, and may include a photoinitiator, a hardener, and the like.
Examples of the photoinitiator include acetophenones, benzophenones, Michler's ketones, benzoin, benzylmethyl acetal, benzamyl benzoate, α-fluorenyl oxime ester, and sulfur Photo radical polymerization initiators such as thioxanthone or photocationic polymerization initiators such as onium salts, sulfonates, and organometallic complexes. Among them, it is difficult to cause side reactions such as ring-opening polymerization of the glycidyl group in the easily-adhesive layer 20 described above, and to effectively polymerize a photopolymerizable prepolymer or a photopolymerizable monomer having a (meth) acrylfluorenyl group. Free radical polymerization initiators are particularly suitable for use.
Moreover, a hardening | curing agent can mix | blend resin suitable for compounds, such as a polyisocyanate, an amine resin, an epoxy resin, and a carboxylic acid, and it can use suitably.

In addition, the functional layer 30 may suitably contain an antistatic agent, an antioxidant, a leveling agent, an anti-blocking agent, a slip agent, a flame retardant, an ultraviolet absorber, a dispersant, and an agglomerating agent as long as the function of the present invention is not hindered. , Pigments, dyes, lubricants and other additives.

The thickness of the functional layer 30 is 0.01 μm or more and 100 μm or less, preferably 1 μm or more and 10 μm or less, and more preferably 2 μm or more and 5 μm or less. By having such a thickness, the adhesion between the functional layer 30 and the easy-adhesion layer 20 is improved, and sufficient adhesion can be maintained even when exposed to a severe environment such as high temperature and high humidity for a long time.
The thickness of the functional layer 30 is measured by, for example, a reflection spectrometer (FE-300UV: Otsuka Electronics Co., Ltd.).

The function of the functional layer 30 is not particularly limited, and may be based on, for example, an anti-glare layer, a hard coating layer, an anti-reflection layer, an antifouling layer, an antibacterial layer, a barrier layer, a light-shielding layer, an index matching layer, and an antistatic layer. Suitable for other purposes. For example, the hard coating layer has a large shrinkage property, and the case where the function of adhesion is not damaged is selected. By satisfying the conditions of the easy-adhesion layer 20 and the functional layer 30 of the present invention, the density can be effectively improved.着 性。 Sex.

Next, the back coating layer 40 will be described. The functional members of the present invention are laminated on at least one side of the substrate in the order of the easy-to-adhere layer 20 and the functional layer 30, respectively, but a back coating layer 40 may be provided if necessary. The back coat layer 40 is not particularly limited, and a layer having necessary functions can be suitably used depending on the application. The back coating layer 40 may be provided with the easy-adhesion layer 20 and the functional layer 30, or a surface treatment may be performed between the substrate 10 and the back coating layer 40.

Next, an example of a method for manufacturing the functional member of the present invention will be described. The manufacturing method of the functional member of the present invention is not particularly limited. For example, on any substrate 10, the material of the easy-adhesion layer 20 is dissolved or dispersed in a suitable solvent by a conventional method, and the coating solution is coated with a coating solution for the easy-adhesion layer. The cloth is produced on the substrate 10, dried, and irradiated with ionizing radiation such as ultraviolet rays if necessary. On the easy-adhesion layer 20, a coating solution for a functional layer in which the material of the functional layer 30 is dissolved or dispersed in an appropriate solvent is applied by a conventional method, and after drying, if necessary, it is irradiated with ionizing radiation such as ultraviolet rays to Production.

In addition, when the back coat layer 40 is provided, the back coat layer for dissolving or dispersing in an appropriate solvent is applied by a conventional method on the side opposite to the functional layer 30 of the base material 10 having the organic energy layer 30. The liquid is prepared by drying and, if necessary, irradiating with ionizing radiation such as ultraviolet rays.

The coating method (film-forming method) of the easy-adhesion layer 20, the functional layer 30, and the back coating layer 40 is not particularly limited. For example, a spin coating method, an extrusion die coating method, a doctor blade coating method, or a bar coating method can be used. , Well-known coating methods such as screen printing method, stencil printing method, roll coating method, spray coating method, dip coating method, inkjet method, and the like.

In this case, from the viewpoint of productivity and the like, the application order of the easy-adhesion layer 20, the functional layer 30, and the back coat layer 40 can be appropriately selected.
If necessary, the functional layer 30 or the back coating layer 40 may be further laminated and coated with the functional layer.

Next, the characteristics of the functional member of the present invention will be described. The characteristics of the functional member are initial adhesion and adhesion after long-term exposure in a severe environment such as high temperature and high humidity.

Adhesion is based on the checkerboard peeling test specified in JIS K 5400. After the functional member has been manufactured, it is in a state without any treatment (hereinafter referred to as the "initial adhesion test") and the accelerated weather resistance test is at a temperature of 85. The test is performed under two types of states after exposure for a certain period of time under an environment with a humidity of 85% (humidity is performed with pure water) (hereinafter referred to as "high temperature and high humidity adhesion test"). Among the 100 squares of the checkerboard, 80 or more of the 100 squares were found to be qualified.

When the functional member according to the present invention is used, the adhesion between the substrate 10 and the easy-adhesion layer 20 and the adhesion between the easy-adhesion layer 20 and the functional layer 30 can be improved. In particular, it has little change over time due to long-term exposure under severe environments such as high temperature and high humidity, and maintains good adhesion.

[Example]

Hereinafter, examples and comparative examples of the functional member of the present invention will be described. In the following examples and comparative examples, unless otherwise specified, "%" and "part" are based on weight.

[Example 1]
A corona discharge treatment was applied to one surface of a 100-m-thick polyethylene terephthalate film (lumirror T60: Toray), and the surface-treated surface was coated with a coating solution for an easy-adhesion layer as shown in Table 1. A. An easy-adhesive layer having a thickness of 1.5 μm is formed by drying. Next, a coating solution A for a functional layer shown in Table 2 was applied on the easy-adhesive layer, and dried, and then irradiated with ultraviolet rays to harden to form a functional layer having a thickness of 3 μm, and a functional member of Example 1 was produced.

＜ Production of Polyester Resin A Water Dispersion ＞
83 parts of terephthalic acid, 36 parts of isophthalic acid, 32 parts of ethylene glycol, and 46 parts of neopentyl glycol were put into a flask equipped with a nitrogen introduction tube, a thermometer, a stirrer, and a still, and heated at 260 ° C for 4 hours. An esterification reaction is performed. Next, 0.1 part of antimony trioxide was added as a catalyst, and the temperature of the system was raised to 280 ° C., and the pressure of the system was gradually reduced to become 0.1 mmHg after 1.5 hours. Under these conditions, a polycondensation reaction was performed for another 4 hours. As a result, a polyester resin A having a molecular weight of 18,400 was obtained. The obtained polyester resin A (25 parts) was put into a mixed solution of 15 parts of isopropyl alcohol and 60 parts of ion-exchanged water, and stirred at 70 to 80 ° C for 3 hours to obtain a polyester resin A having a solid content concentration of 25%. Water dispersion. The solid content acid value of the polyester resin A aqueous dispersion was 1.0 mgKOH / g.

＜ Production of Polyester Resin B Water Dispersion ＞
77 parts of dimethyl terephthalate, 50 parts of dimethyl isophthalate, 47 parts of ethylene glycol, 73 parts of neopentyl glycol, 0.1 part of zinc acetate as a catalyst, and antimony trioxide 0.1 part was put into a flask equipped with a nitrogen introduction tube, a thermometer, a stirrer and a still, and heated at 140 to 220 ° C for 3 hours to perform a transesterification reaction. Next, the polycondensation reaction was carried out under reduced pressure (10 to 0.2 mmHg) at 240 to 270 ° C for 30 minutes. Next, 15 parts of trimellitic anhydride was added at 170 to 190 ° C under normal pressure, and an addition reaction was performed for 30 minutes. As a result, a polyester resin B having a molecular weight of 5,700 was obtained. The obtained polyester resin B (25 parts) was put into a mixed solution of 15 parts of isopropyl alcohol and 60 parts of ion-exchanged water, and stirred at 70 to 80 ° C for 3 hours to obtain a polyester resin B having a solid content concentration of 25%. Water dispersion. The solid content acid value of the polyester resin B aqueous dispersion was 42 mgKOH / g.

＜ Production of Polyester Resin C Water Dispersion ＞
83 parts of terephthalic acid, 83 parts of isophthalic acid, 62 parts of ethylene glycol, 21 parts of ethylene glycol, and 0.1 part of zinc acetate as a catalyst were put into a unit equipped with a nitrogen introduction tube, a thermometer, a stirrer, and a still. The flask was heated at 190-220 ° C for 13 hours to perform an esterification reaction to obtain polyester glycol. 100 parts of the obtained polyester diol, 100 parts of xylene, and 28 parts of pyromellitic anhydride were put into a flask equipped with the same apparatus as above, and after reacting at 140 ° C. for 1 hour, the xylene was distilled off, and the temperature of the system was spent. After 2 hours, the temperature was raised to 180 ° C, and the temperature was maintained for 1 hour. As a result, a polyester resin C having a molecular weight of 18,000 was obtained. The obtained polyester resin C (25 parts) was put into a mixed solution of 15 parts of isopropyl alcohol and 60 parts of ion-exchanged water, and stirred at 70 to 80 ° C for 3 hours to obtain a polyester resin C having a solid content concentration of 25%. Water dispersion. The solid content acid value of the polyester resin C aqueous dispersion was 110 mgKOH / g.

＜ Production of acrylic resin A water dispersion ＞
Put 18 parts of ion-exchanged water and 3 parts of ELEMINOL RS-3000 (Sanyo Chemical Co., Ltd., anionic surfactant, 50% solids concentration) into the beaker, stir and add 40 parts of glycidyl methyl acrylate while stirring, make a single Body emulsion. Next, a flask equipped with a condenser, a funnel for dropping monomers, a thermometer, and a stirrer was charged with 37.5 parts of ion-exchanged water, ELEMINOL RS-3000 (1 part), and 0.5 parts of potassium persulfate, followed by stirring and nitrogen substitution. The heating was started, and the monomer emulsion was dropped at 75 ° C over 4 hours. After the dripping was completed, the solution was stirred at 75-85 ° C for 4 hours, and then cooled. After cooling, ion-exchanged water was further added to obtain a glycidyl-containing acrylic resin A aqueous dispersion having a solid content concentration of 25%. The solid content acid value of the acrylic resin A aqueous dispersion was 0.33 mgKOH / g.

＜ Production of acrylic resin B water dispersion ＞
Put 18 parts of ion-exchanged water and 3 parts of ELEMINOL RS-3000 (Sanyo Chemical Co., Ltd., anionic surfactant, 50% solids concentration) into the beaker, and stir while adding 71 parts of methyl methacrylate and butyl acrylate. 29 parts to prepare a monomer emulsion. Next, a flask equipped with a condenser, a funnel for dropping monomers, a thermometer, and a stirrer was charged with 37.5 parts of ion-exchanged water, ELEMINOL RS-3000 (1 part), and 0.5 parts of potassium persulfate, followed by stirring and nitrogen substitution. The heating was started, and the monomer emulsion was dropped at 75 ° C over 4 hours. After the dripping was completed, the solution was stirred at 75-85 ° C for 4 hours, and then cooled. After cooling, ion-exchanged water was further added to obtain a 25% solids concentration acrylic acid resin B aqueous dispersion without glycidyl group. The solid content acid value of the acrylic resin B aqueous dispersion was 0.50 mgKOH / g.

[Example 2]
A functional member of Example 2 was produced in the same manner as in Example 1 except that the corona discharge treatment of Example 1 was not applied.

[Example 3]
A functional member of Example 3 was produced in the same manner as in Example 1 except that the coating solution A for an easy-adhesive layer of Example 1 was changed to the coating solution B for an easy-adhesive layer described in Table 1.

[Example 4]
A functional member of Example 4 was produced in the same manner as in Example 1 except that the coating solution A for the easy-adhesive layer of Example 1 was changed to the coating solution C for the easy-adhesive layer described in Table 1.

[Example 5]
A functional member of Example 5 was produced in the same manner as in Example 1 except that the coating solution A for functional layers of Example 1 was changed to the coating solution B for functional layers described in Table 2.

[Example 6]
A functional member of Example 6 was produced in the same manner as in Example 1 except that the coating solution A for functional layers of Example 1 was changed to the coating solution C for functional layers described in Table 2.

[Example 7]
A functional member of Example 7 was produced in the same manner as in Example 1 except that the coating solution A for functional layers of Example 1 was changed to the coating solution D for functional layers described in Table 2.

[Example 8]
A functional member of Example 8 was produced in the same manner as in Example 1 except that the coating solution A for functional layers of Example 1 was changed to the coating solution E for functional layers described in Table 2.

[Comparative Example 1]
A functional member of Comparative Example 1 was produced in the same manner as in Example 1 except that the coating solution A for the easy-adhesive layer of Example 1 was changed to the coating solution D for the easy-adhesive layer described in Table 1.

[Comparative Example 2]
A functional member of Comparative Example 2 was produced in the same manner as in Example 1 except that the coating solution A for functional layers in Example 1 was changed to the coating solution F for functional layers described in Table 2.

[Comparative Example 3]
A functional member of Comparative Example 3 was produced in the same manner as in Example 1 except that the coating solution A for the easy-adhesive layer of Example 1 was changed to the coating solution E for the easy-adhesive layer described in Table 1.

[Comparative Example 4]
A functional member of Comparative Example 4 was produced in the same manner as in Example 1 except that the coating solution A for easy-adhesive layer of Example 1 was changed to the coating solution F for easy-adhesive layer described in Table 1.

[Comparative Example 5]
A functional member of Comparative Example 5 was produced in the same manner as in Example 1 except that the coating solution A for the easy-adhesive layer of Example 1 was changed to the coating solution G for the easy-adhesive layer described in Table 1.

[Comparative Example 6]
A functional member of Comparative Example 6 was produced in the same manner as in Example 1 except that the coating solution A for the easy-adhesive layer of Example 1 was changed to the coating solution H for the easy-adhesive layer described in Table 1.

The coating liquid for an easy-to-adhesive layer, the coating liquid for a functional layer, and a functional member produced in the above examples and comparative examples were evaluated for the following characteristics.

＜ Calculation of acid value of solid content ＞
For the coating liquids for the easy-adhesive layers and the coating liquids for the functional layers of Examples 1 to 8 and Comparative Examples 1 to 6 described above, the acids obtained in accordance with the indicator titration method specified in JIS K 2501: 2003 The value calculated by the valence and the respective solid content concentration is taken as the solid content acid value. The calculation results are shown in Table 3.

＜ Adhesion test ＞
1. Initial Adhesion Test The functional layers of the functional members prepared in the above examples and comparative examples were tested in accordance with the checkerboard peel test specified in JIS K 5400, and evaluated on the basis shown below. Among all the 100 squares of the checkerboard, no more than a quarter of the cells were peeled off, and it was evaluated as "◎". Among the 100 squares, there were no quarters among the 80 squares or more. One or more peeling states were evaluated as "0", and among 100 squares, the state in which no more than a quarter of the peeling cells did not reach 80 squares was evaluated as "X". The measurement results are shown in Table 3.

2. Adhesion test after high-temperature and high-humidity exposure The functional members prepared in the above examples and comparative examples were exposed to an environment at a temperature of 85 ° C. and a humidity of 85% (humidification was performed with pure water) for 500 hours. Then, the functional layer was tested in accordance with the checkerboard peel test specified in JIS K 5400, and evaluated on the basis shown below. Among all the 100 squares of the checkerboard, no more than a quarter of the cells were peeled off, and it was evaluated as "◎". Among the 100 squares, there were no quarters among the 80 squares or more. One or more peeling states were evaluated as "0", and among 100 squares, the state in which no more than a quarter of the peeling cells did not reach 80 squares was evaluated as "X". The measurement results are shown in Table 3.

From the results in Table 3, it can be seen that the functional members of Examples 1 to 8 were formed of a polyester-acrylic composite resin having a glycidyl group because the composition for forming an easy-adhesive layer on the substrate was a solid component of the composition. The acid value is 2.5 to 6.0 mgKOH / g, and the composition for forming the aforementioned functional layer includes a compound having a functional group reactive with a glycidyl group, and the solid component acid value of the composition is less than 4.0 mgKOH / g, Therefore, the initial adhesion test and the adhesion test after high temperature and high humidity exposure are all evaluated well, and the adhesion between the substrate and the easy-adhesion layer and the adhesion between the easy-adhesion layer and the functional layer are excellent.

In contrast, Comparative Example 1 and Comparative Example 6 did not contain a compound having a glycidyl group because the composition for forming an easy-adhesive layer did not exhibit the adhesion between the base material and the easy-adhesive layer, and the closeness between the easy-adhesive layer and the functional layer. Adhesive addition reaction, the initial adhesiveness and adhesiveness after exposure to high temperature and high humidity are poor. In Comparative Example 1 and Comparative Example 4, since the solid component acid value of the composition for forming an easy-adhesive layer was less than 2.5 mgKOH / g, the addition reaction exhibiting the aforementioned adhesion did not proceed sufficiently, and the initial adhesion and Poor adhesion after high temperature and high humidity exposure. In Comparative Example 3 and Comparative Example 5, since the acid value of the solid content of the composition for forming an easy-to-adhesive layer exceeds 6.0 mgKOH / g, side reactions such as ring-opening polymerization of glycidyl group are preferred, and the aforementioned adhesion is exhibited. The formation reaction is hindered, and the initial adhesiveness and / or the adhesiveness after high temperature and high humidity exposure are poor. Comparative Example 2 shows that the solid component acid value of the composition for forming an easy-adhesive layer is in a good range, but the solid component acid value of the composition for forming a functional layer exceeds 4.0 mgKOH / g, so it exhibits the aforementioned adhesiveness. The addition reaction did not proceed sufficiently, and therefore the adhesion was poor after exposure to high temperature and high humidity. In addition, Comparative Example 1 has a low concentration of acryl fluorene-based components, which forms a composition for forming an easy-adhesive layer. Therefore, initial adhesion and adhesion after exposure to high temperature and high humidity are poor. Comparative Example 5 is a composition for forming an easy-adhesive layer. The concentration of the acryl fluorene-based component of the material is too high, so the adhesion is poor after exposure to high temperature and high humidity.

10‧‧‧ Substrate

20‧‧‧ Easy to attach layer

30‧‧‧functional layer

40‧‧‧back coating

[Fig. 1] A basic form of a functional member of the present invention.

[Fig. 2] In the functional member of the present invention, a form in which a back coat is applied on the surface opposite to the surface on which the organic energy layer is formed.

Claims (6)

A functional member is a functional member laminated on at least one side of a substrate in the order of an easy-adhesive layer and a functional layer. The composition for forming the easy-adhesive layer includes a polyester-acrylic composite resin having a glycidyl group. And the solid component has an acid value of 2.5 to 6.0 mgKOH / g, the composition for forming the foregoing functional layer includes a compound having a functional group reactive with a glycidyl group, and the solid component has an acid value It is 4.0 mgKOH / g or less. For example, the functional component of claim 1, wherein the composition for forming the aforementioned easy-adhesive layer is a composition containing the aforementioned polyester-acrylic composite resin as a main component. For example, the functional component of claim 1 or 2, wherein the content of the acrylic resin component in all the constituent components of the entire solid component forming the composition for the easy-adhesion layer is 20 to 50% by weight. The functional component according to any one of claims 1 to 3, wherein the functional group reactive with the glycidyl group is a hydroxyl group. The functional member according to any one of claims 1 to 4, wherein the surface on which the aforementioned substrate is laminated with the easily-adhesive layer is a functional group that is introduced with a glycidyl group by surface treatment. The functional component according to claim 5, wherein the functional group having reactivity with the glycidyl group introduced by the aforementioned surface treatment is a hydroxyl group.