JP7042661B2 - Functional member - Google Patents

Description

The present invention relates to a functional member, a film, a sheet, etc. in which a base material, an easy-adhesion layer, and a functional layer are laminated in this order, and more specifically, a function of maintaining sufficient adhesion even in a harsh environment such as high temperature and high humidity. It relates to sex members, films, sheets, etc.

Plastic materials are widely used as materials for electronic devices due to their light weight, processing suitability, and productivity. The plastic material may be used alone, but in many cases, a functional layer having a specific function is laminated on the surface, and a function according to the application is added. Especially in recent years, the use of plastic materials has advanced to fields that have not been used in the past as replacements for glass and metal materials, and along with this, plastic materials also have high interlayer adhesion stability in harsh environments such as high temperature and high humidity. It has come to be required.

Japanese Unexamined Patent Publication No. 09-176518 International Publication 2015/170560

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, sheets, etc., but the surface thereof is crystallized. In many cases, the adhesiveness of ink, adhesive, etc. is poor. Among them, in the case of a film, it is known that the level of adhesiveness is very low and the adhesiveness is generally inferior because the crystal is highly oriented by the steps of stretching and heat fixing.

In such a case, a material having a high affinity with the plastic film can be used for the functional layer, but the material of the functional layer is extremely limited and the necessary functions may be impaired. Therefore, as in Patent Document 1 and Patent Document 2, by providing an easy-adhesive layer having high affinity with both layers between the base material and the functional layer, the adhesion between the base material and the easy-adhesive layer and the function with the easy-adhesive layer are provided. Techniques have been taken to improve the adhesion of the layers. However, even with such a functional plastic film provided with an easy-adhesive layer, although the initial adhesion is good, if the film is exposed for a long time in a harsh environment such as high temperature and high humidity, The adhesion between the base material and the easy-adhesion layer and / or the adhesion between the easy-adhesion layer and the functional layer is deteriorated, and problems such as peeling of the easy-adhesion layer and / or the functional layer occur.

As mentioned above, in recent years, fields that have not been used until now, such as transparent conductive substrates for touch panels, flexible circuit boards, substrates for flexible displays, substrates for organic EL, substrates for LED lighting, etc. A plastic material is also used as the material of the device, and high initial adhesion and stability over time in a harsh environment such as high temperature and high humidity, which have not been required in the past, are required.

The present invention improves the adhesion between the base material and the easy-adhesion layer and the adhesion between the easy-adhesion layer and the functional layer, and maintains sufficient adhesion even when exposed for a long time in a harsh environment such as high temperature and high humidity. The purpose is.

The functional member of the present invention is a functional member in which an easy-adhesion layer and a functional layer are laminated in this order on at least one surface of a base material, and the composition for forming the easy-adhesion layer has a glycidyl group. A functional group containing a polyester-acrylic composite resin, having a solid acid value of 2.5 to 6.0 mgKOH / g, and having a reactivity with a glycidyl group in the composition for forming the functional layer. It is characterized by containing a compound having a above-mentioned substance and having a solid acid value of 4.0 mgKOH / g or less of the composition.

Further, the functional member of the present invention is characterized in that the composition for forming the easy-adhesion layer preferably contains the polyester-acrylic composite resin as a main component.

Further, the functional member of the present invention is characterized in that the content of the acrylic resin component in the total solid content of the composition for forming the easy-adhesion layer is preferably 20 to 50% by weight. And.

Further, the functional member of the present invention is preferably characterized in that the functional group having reactivity with the glycidyl group is a hydroxy group.

Further, the functional member of the present invention is preferably characterized in that a functional group having reactivity with a glycidyl group is introduced into the surface of the base material on which the easy-adhesion layer is laminated by surface treatment. And.

Further, the functional member of the present invention is characterized in that the functional group having reactivity with the glycidyl group introduced by the surface treatment is preferably a hydroxy group.

According to the present invention, it is possible to improve the adhesion between the base material of the functional member and the easy-adhesion layer and the adhesion between the easy-adhesion layer and the functional layer. In particular, even in a harsh environment such as high temperature and high humidity, the functional member has little change in adhesion and good adhesion is maintained.

Basic form of the functional member of the present invention In the functional member of the present invention, a backcoat layer is applied to a surface opposite to the surface on which the functional layer of the base material is formed.

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

As shown in FIG. 1, the functional member of the present invention has a base material 10, an easy-adhesion layer 20, and a functional layer 30 as a basic configuration. The functional member is not limited to the one shown in FIG. 1, and may be provided with a back coat layer 40 (FIG. 2) on a surface opposite to the surface on which the functional layer 30 is laminated.

First, the base material 10 will be described. As the base material 10, a plastic film is preferably used. As the plastic film, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, triacetyl cellulose, polymethyl methacrylate, polyvinyl chloride, polynorbornene, polyimide compounds and the like can be used, for example, transparency. , The base material can be selected according to the application such as heat resistance, mechanical strength, dimensional stability, and color. Among them, a stretched polyethylene terephthalate film, particularly a biaxially stretched polyethylene terephthalate film, is preferably used because of its excellent mechanical strength and dimensional stability.

The thickness of the base material 10 is not particularly limited and can be appropriately selected depending on the material to be applied, but is generally 1 μm or more and 300 μm or less, preferably 23 μm or more and 188 μm or less in consideration of handleability.

The base material 10 may be subjected to surface treatment such as plasma treatment, corona discharge treatment, and far ultraviolet irradiation treatment depending on the case. By applying these surface treatments, the wettability of the easy-adhesion layer 20 to the base material 10 is improved, and the adhesion is improved. In particular, when the functional group introduced by the plasma treatment or the corona discharge treatment is a functional group having reactivity with the glycidyl group, an addition reaction occurs with the glycidyl group of the easy-adhesion layer 20 described later, and the adhesion is further improved.

Here, examples of the functional group having a reactivity with the glycidyl group introduced by the surface treatment include a hydroxy group, a carboxy group, a hydroperoxy group, a carbonyl group, an epoxy group and the like, and the functional group is preferably a hydroxy group. Is desirable.

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 contains a polyester-acrylic composite resin having a glycidyl group and has a specific solid content acid value, and is an ionizing radiation curable resin and a thermosetting resin. Compounds such as curable resin and thermoplastic resin can be used alone or in combination of two or more, and can be used properly according to the purpose.

Although the mechanism of adhesion is not certain, the composition for forming the easy-adhesion layer 20 contains a polyester-acrylic composite resin having a specific solid acid value and a glycidyl group, and the functional layer 30 described later. The composition for forming the above contains a compound having a specific solid acid value and a functional group reactive with a glycidyl group, so that an addition reaction occurs between the easy-adhesion layer 20 and the functional layer 30. It is considered that the adhesion between the adhesive layer 20 and the functional layer 30 is improved.
The adhesion to the base material 10 differs depending on the material of the base material 10, but if the adhesion is not sufficient, the adhesion can be improved by applying the above-mentioned surface treatment to the base material 10.
Further, 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, further improving the adhesion. Let me.

The solid acid value of the composition for forming the easy-adhesion layer 20 is 2.5 mgKOH / to improve the adhesion between the base material 10 and the easy-adhesion layer 20 and the adhesion between the easy-adhesion layer 20 and the functional layer 30. It is preferably g or more, more preferably 3.0 mgKOH / g or more, preferably 6.0 mgKOH / g or less, 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 reactive with the glycidyl group and the glycidyl group does not proceed sufficiently, so that the adhesion between the base material 10 and the easy-adhesion layer 20 does not proceed sufficiently. In addition, the adhesion between the easy-adhesion layer 20 and the functional layer 30 may decrease, and if it is larger than 6.0 mgKOH / g, side reactions such as ring-opening polymerization of the glycidyl group are prioritized and the addition reaction is inhibited. There may be a problem that the adhesion between the base material 10 and the easy-adhesion layer 20 and the adhesion between the easy-adhesion layer 20 and the functional layer 30 are deteriorated.
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 the solid content concentration thereof.

The acid value of the composition for forming the easy-adhesion layer 20 is adjusted by introducing a functional group such as a carboxy group, a sulfo group, a phosphoric acid group, or a phenolic hydroxy group into the compound constituting the composition. can do.

It is desirable that the composition contains a polyester-acrylic composite resin as a main component. By using the polyester-acrylic composite resin as a main component, the adhesion between the base material 10 and the easy-adhesion layer 20 and the adhesion between the easy-adhesion layer 20 and the functional layer 30 can be improved.
The main component in the present invention means that when the total solid content of the components constituting the composition is 100 parts by weight, the component 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 may be a composite thereof. Examples of the compound containing both the polyester component and the acrylic component as constituent components include a polyester-acrylic copolymer and the like. Considering the storage stability of the composition and the transparency and smoothness of the film, it is desirable that the compound contains both the polyester component and the acrylic component as constituent components.

The component ratio of the composition for forming the easy-adhesive layer 20 is not necessarily limited, but when the content of the acrylic resin component in the constituent components of the total solid content is in the range of 20 to 50% by weight, the base material 10 is used. The adhesion between the easy-adhesion layer 20 and the easy-adhesion layer 20 and the functional layer 30 are further improved.

The content of the glycidyl group of the polyester-acrylic composite resin can be expressed by the number of grams of the compound containing 1 gram equivalent of the epoxy group, that is, the epoxy equivalent.
The epoxy equivalent in the polyester-acrylic composite resin is 100 g / eq. In order to improve the adhesion between the easy-adhesion layer 20 and the functional layer 30. The above is preferable, and more preferably 120 g / eq. As mentioned above, the most preferable is 150 g / eq. With the above, 100,000 g / eq. Hereinafter, more preferably 10,000 g / eq. Hereinafter, most preferably 5000 g / eq. It is as follows. By satisfying this range, sufficient adhesion is maintained even in the initial adhesion and long-term exposure in a harsh environment such as high temperature and high humidity.
The epoxy equivalent is 100 g / eq. If it is less than, the rigidity and toughness of the easy-adhesion layer 20 are insufficient, and the adhesion between the base material 10 and the easy-adhesion layer 20 and / or the adhesion between the easy-adhesion layer 20 and the functional layer 30 is lowered. In addition, 100,000 g / eq. If it exceeds, the content of the glycidyl group is too small, and the amount of chemical bonds formed by the addition reaction between the base material 10 and the easy-adhesion layer 20 and between the easy-adhesion layer 20 and the functional layer 30 is not sufficient. When exposed for a long time in a harsh environment such as high temperature and high humidity, a peeling defect occurs between the base material 10 and the easy-adhesive layer 20 and / or between the easy-adhesive layer 20 and the functional layer 30.
Epoxy equivalents can be determined by the method specified in JIS K 7236: 2009.

Further, the easy-adhesion layer 20 has an antistatic agent, an antioxidant, a leveling agent, an antiblocking agent, a slip agent, a flame retardant, an ultraviolet absorber, a dispersant, a flocculant, and a pigment within a range that does not impair the function of the present invention. , Dyes, lubricants and other additives can also be appropriately contained.

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 adhesiveness between the base material 10 and the easy-adhesive layer 20 and the adhesiveness between the easy-adhesive layer 20 and the functional layer 30 are improved, and in a long-term exposure in a harsh environment such as high temperature and high humidity. However, sufficient adhesion is maintained.
The thickness of the easy-adhesion layer 20 is measured by, for example, a reflection spectroscopic film thickness meter (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 contains a functional group reactive with a glycidyl group and has a specific solid content acid value, and is an ionizing radiation curable resin and a thermosetting resin. Compounds such as resins and thermoplastic resins can be used alone or in combination of two or more, and can be used properly according to the purpose.

As such an ionizing radiation curable resin, ionizing radiation (ultraviolet rays or electron beams) is applied to an ionizing radiation curable coating material obtained by mixing one or more of a photopolymerizable prepolymer or a photopolymerizable monomer. You can use the one that cures with. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having one or more (meth) acryloyl groups in one molecule is particularly preferably used. Examples of the acrylic prepolymer include urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate, polyperfluoroalkyl acrylate, and silicone acrylate.

Further, as the photopolymerizable monomer, an acrylic monomer having one or two or more (meth) acryloyl groups in one molecule is particularly preferably used. For example, monofunctional acrylic monomers such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-butoxyethyl acrylate; for example, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol di. Bifunctional acrylic monomers such as acrylates, polyethylene glycol diacrylates and neopentyl glycol diacrylates hydroxypivalate; for example, polyfunctional (trifunctional or higher) acrylics such as dipentaerythritol hexaacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate and the like. Monomer; and the like. These photopolymerizable monomers can be used alone or in combination of two or more. The blending ratio of the photopolymerizable prepolymer and the photopolymerizable monomer is not particularly limited, and is appropriately set according to the purpose and application.

Examples of the thermosetting resin include polyester acrylate resin, polyurethane acrylate resin, epoxy acrylate resin, epoxy resin, melamine resin, phenol resin, silicone resin and the like.

Examples of the thermoplastic resin include polyester resin, acrylic resin, polycarbonate resin, cellulose resin, acetal resin, vinyl resin, polyethylene resin, polystyrene resin, polypropylene resin, polyamide resin, and polyimide. Examples thereof include based resins and fluororesins.

The functional group having a reactivity with the glycidyl group of the easy-adhesion layer 20 contained in the composition for forming the functional layer 30 is not particularly limited, but for example, a hydroxy group, an amino group, a carboxy group and a carboxylic acid. An anhydride, an imidazole group, a mercapto group, an isocyanate group and the like can be used.
A hydroxy group is particularly desirable in consideration of the ease of controlling the reaction during production.

The solid acid value of the composition for forming the functional layer 30 is preferably 4.0 mgKOH / g or less, more preferably 3.0 mgKOH / g, in order to further improve the adhesion between the easy-adhesion layer 20 and the functional layer 30. It is less than or equal to g. If the acid value exceeds 4.0 mgKOH / g, side reactions such as ring-opening polymerization of the glycidyl group in the easy-adhesion layer 20 are prioritized, and an addition reaction for exhibiting the adhesion is inhibited. There are cases.
The solid acid value can be determined by the same method as the solid acid value of the composition for forming the easy-adhesion layer 20 described above.

The functional layer 30 may further contain a photoinitiator, a curing agent, or the like depending on the curing method.
Examples of the photoinitiator include photoradical polymerization initiators such as acetophenones, benzophenones, Michler ketone, benzoin, benzylmethylketal, benzoylbenzoate, α-acyloxime ester, and thioxanthones, onium salts, sulfonic acid esters, and organic metal complexes. Examples thereof include a photocationic polymerization initiator. Above all, a photoradical polymerization initiator that is less likely to cause side reactions such as ring-opening polymerization of the glycidyl group in the easy-adhesion layer 20 and effectively polymerizes a photopolymerizable prepolymer having a (meth) acryloyl group or a photopolymerizable monomer. Is particularly preferably used.
Further, as the curing agent, compounds such as polyisocyanate, amino resin, epoxy resin and carboxylic acid can be appropriately used according to the compatible resin.

Further, the functional layer 30 contains antistatic agents, antioxidants, leveling agents, antiblocking agents, slip agents, flame retardants, ultraviolet absorbers, dispersants, flocculants, pigments, as long as the functions of the present invention are not impaired. Additives such as dyes and lubricants can also be appropriately contained.

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 functional layer 30 improves the adhesiveness with the easy-adhesive layer 20, and sufficient adhesiveness is maintained even in a long-term exposure in a harsh environment such as high temperature and high humidity.
The thickness of the functional layer 30 is measured, for example, by a reflection spectroscopic film thickness meter (FE-300UV: Otsuka Electronics Co., Ltd.).

The function of the functional layer 30 is not particularly limited, but for example, an antiglare layer, a hard coat layer, an antireflection layer, an antifouling layer, an antibacterial layer, a barrier layer, a light shielding layer, an index matching layer, an antistatic layer, and the like can be used depending on the purpose. Can be selected as appropriate. Even when a function such as a hard coat layer in which the adhesiveness is impaired due to the large shrinkage of the film is selected, the adhesiveness is effectively satisfied by satisfying the conditions of the easy-adhesion layer 20 and the functional layer 30 of the present invention. Can be improved.

Next, the back coat layer 40 will be described. In the functional member of the present invention, the easy-adhesive layer 20 and the functional layer 30 are laminated in this order on at least one surface of the base material, respectively, but a back coat layer 40 may be provided if necessary. .. The backcoat layer 40 is not particularly limited, and a layer having a necessary function can be appropriately used depending on the application. The easy-adhesive layer 20 and the functional layer 30 may be provided as the backcoat layer 40, or a surface treatment may be applied between the base material 10 and the backcoat layer 40.

Next, an example of the method for manufacturing the functional member of the present invention will be described. The method for producing the functional member of the present invention is not particularly limited, and for example, a coating liquid for an easy-adhesive layer obtained by dissolving or dispersing the above-mentioned material of the easy-adhesive layer 20 in an appropriate solvent on an arbitrary base material 10 is known. It can be produced by applying and drying on the base material 10 by the method of the above method, and irradiating ionizing radiation such as ultraviolet rays as necessary. Further, on the easy-adhesion layer 20, a coating liquid for a functional layer in which the above-mentioned material of the functional layer 30 is dissolved or dispersed in an appropriate solvent is applied by a known method, dried, and ionized by ultraviolet rays or the like as necessary. It can be manufactured by irradiating it with radiation.

Further, when the back coat layer 40 is provided, a coating liquid for a back coat layer, which is dissolved or dispersed in an appropriate solvent, is known on the surface of the base material 10 provided with the functional layer 30 on the opposite side of the functional layer 30. It can be manufactured by applying and drying by the method of the above method, and irradiating with ionizing radiation such as ultraviolet rays as needed.

The coating method (deposition method) of the easy-adhesion layer 20, the functional layer 30 and the backcoat layer 40 is not particularly limited, and for example, a spin coating method, an extrusion die coating method, a blade coating method, a bar coating method, and a screen printing method. , A known coating method such as a stencil printing method, a roll coating method, a spray coating method, a dip coating method, and an inkjet method can be used.

At this time, the coating order of the easy-adhesion layer 20, the functional layer 30, and the backcoat layer 40 can be appropriately selected from the viewpoint of productivity and the like.
Further, if necessary, the functional layer may be further laminated and coated on the functional layer 30 or the backcoat layer 40.

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

Adhesion is based on the grid peeling test specified by JIS K 5400, and the state where nothing is processed after the functional member is manufactured (hereinafter referred to as "initial adhesion test") and the accelerated weather resistance test. The test was conducted in two types of conditions after exposure for a certain period of time in an environment with a temperature of 85 ° C and a humidity of 85% (humidification is performed with pure water) (hereinafter referred to as "adhesion test after high temperature and high humidity exposure"). , A state in which no peeling of 1/4 or more is observed in 80 or more squares out of 100 squares on the board of various test pieces is regarded as passing.

According to the functional member of the present invention, the adhesion between the base material 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, there is little change over time due to long-term exposure in a harsh environment such as high temperature and high humidity, and good adhesion is maintained.

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

[Example 1]
One surface of a 100 μm-thick polyethylene terephthalate film (Lumilar T60: Toray Industries, Inc.) was subjected to corona discharge treatment, and the surface-treated surface was coated with the coating liquid A for an easy-adhesive layer of the formulation shown in Table 1 and dried. An easy-adhesive layer having a thickness of 1.5 μm was formed. Next, the coating liquid A for the functional layer according to the formulation shown in Table 2 was applied onto the easy-adhesive layer, dried, and then irradiated with ultraviolet rays to cure the functional layer to form a functional layer having a thickness of 3 μm. A member was produced.

<Manufacturing of polyester resin A aqueous dispersion>
83 parts of terephthalic acid, 36 parts of isophthalic acid, 32 parts of ethylene glycol and 46 parts of neopentyl glycol are placed in a flask equipped with a nitrogen introduction tube, a thermometer, a stirrer and a distiller, and heated at 260 ° C. for 4 hours for an esterification reaction. Was done. Next, 0.1 part of antimony trioxide was added as a catalyst, the temperature of the system was raised to 280 ° C., and the pressure of the system was gradually reduced to 0.1 mmHg after 1.5 hours. As a result of conducting a polycondensation reaction for another 4 hours under these conditions, a polyester resin A having a molecular weight of 18400 was obtained. 25 parts of the obtained polyester resin A was charged into a mixed solution of 15 parts of isopropanol and 60 parts of ion-exchanged water, and the mixture was stirred at 70 to 80 ° C. for 3 hours to obtain a polyester resin A aqueous dispersion having a solid content concentration of 25%. The solid acid value of the polyester resin A aqueous dispersion was 1.0 mgKOH / g.

<Manufacturing 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 and 0.1 part of antimony trioxide as catalysts, nitrogen introduction tube, thermometer, stirrer and distiller The ester exchange reaction was carried out by charging the flask with the above-mentioned product at 140 to 220 ° C. for 3 hours. Then, the polycondensation reaction was carried out at 240 to 270 ° C. under reduced pressure (10 to 0.2 mmHg) for 30 minutes. Next, 15 parts of anhydrous trimellitic acid was added under normal pressure at 170 to 190 ° C., and an addition reaction was carried out for 30 minutes to obtain a polyester resin B having a molecular weight of 5700. 25 parts of the obtained polyester resin B was charged into a mixed solution of 15 parts of isopropanol and 60 parts of ion-exchanged water, and the mixture was stirred at 70 to 80 ° C. for 3 hours to obtain a polyester resin B aqueous dispersion having a solid content concentration of 25%. The solid acid value of the polyester resin B aqueous dispersion was 42 mgKOH / g.

<Manufacturing of polyester resin C water dispersion>
83 parts of terephthalic acid, 83 parts of isophthalic acid, 62 parts of ethylene glycol, 21 parts of diethylene glycol and 0.1 part of zinc acetate as a catalyst were placed in a flask equipped with a nitrogen introduction tube, a thermometer, a stirrer and a distiller at 190 to 220 ° C. The esterification reaction was carried out by heating for 13 hours to obtain polyester glycol. 100 parts of the obtained polyester glycol, 100 parts of xylene and 28 parts of pyromellitic anhydride were placed in a flask equipped with the same equipment as above, and the reaction was carried out at 140 ° C. for 1 hour. The temperature was raised to 180 ° C. over 2 hours and kept warm for another 1 hour. As a result, a polyester resin C having a molecular weight of 18,000 was obtained. 25 parts of the obtained polyester resin C was charged into a mixed solution of 15 parts of isopropanol and 60 parts of ion-exchanged water, and the mixture was stirred at 70 to 80 ° C. for 3 hours to obtain a polyester resin C aqueous dispersion having a solid content concentration of 25%. The solid acid value of the polyester resin C aqueous dispersion was 110 mgKOH / g.

<Manufacturing of acrylic resin A aqueous dispersion>
Put 18 parts of ion-exchanged water and 3 parts of Eleminor RS-3000 (SANYO CHEMICAL INDUSTRIES, anionic surfactant, solid content concentration 50%) in a beaker, add 40 parts of glycidyl methacrylate while stirring, and add a monomer emulsion. Made. Next, in a flask equipped with a condenser, a funnel for dropping a monomer, a thermometer and a stirrer, 37.5 parts of ion-exchanged water, 1 part of Eleminor RS-3000 and 0.5 part of potassium persulfate were charged, and nitrogen was replaced while stirring. After that, heating was started, and the monomer emulsion was added dropwise at 75 ° C. over 4 hours. After the completion of the dropping, the mixture was stirred at a liquid temperature of 75 to 85 ° C. for 4 hours and then cooled. After cooling, ion-exchanged water was further added to obtain an acrylic resin A aqueous dispersion having a glycidyl group having a solid content concentration of 25%. The solid acid value of the acrylic resin A aqueous dispersion was 0.33 mgKOH / g.

<Manufacturing of acrylic resin B water dispersion>
18 parts of ion-exchanged water and 3 parts of Eleminor RS-3000 (SANYO CHEMICAL INDUSTRIES, anionic surfactant, solid content concentration 50%) were charged in a beaker, and 71 parts of methyl methacrylate and 29 parts of butyl acrylate were added while stirring. , A monomer emulsion was prepared. Next, in a flask equipped with a condenser, a funnel for dropping a monomer, a thermometer and a stirrer, 37.5 parts of ion-exchanged water, 1 part of Eleminor RS-3000 and 0.5 part of potassium persulfate were charged, and nitrogen was replaced while stirring. After that, heating was started, and the monomer emulsion was added dropwise at 75 ° C. over 4 hours. After the completion of the dropping, the mixture was stirred at a liquid temperature of 75 to 85 ° C. for 4 hours and then cooled. After cooling, ion-exchanged water was further added to obtain an acrylic resin B aqueous dispersion having a solid content concentration of 25% and having no glycidyl group. The solid 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 performed.

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

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

[Example 5]
The functional member of Example 5 was produced in the same manner as in Example 1 except that the functional layer coating liquid A of Example 1 was changed to the functional layer coating liquid B shown in Table 2.

[Example 6]
The functional member of Example 6 was produced in the same manner as in Example 1 except that the functional layer coating liquid A of Example 1 was changed to the functional layer coating liquid C shown in Table 2.

[Example 7]
The functional member of Example 7 was produced in the same manner as in Example 1 except that the functional layer coating liquid A of Example 1 was changed to the functional layer coating liquid D shown in Table 2.

[Example 8]
The functional member of Example 8 was produced in the same manner as in Example 1 except that the functional layer coating liquid A of Example 1 was changed to the functional layer coating liquid E shown in Table 2.

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

[Comparative Example 2]
The functional member of Comparative Example 2 was produced in the same manner as in Example 1 except that the functional layer coating liquid A of Example 1 was changed to the functional layer coating liquid F shown in Table 2.

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

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

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

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

Table 1

Table 2

The following characteristics were evaluated for the coating liquid for the easy-adhesive layer, the coating liquid for the functional layer, and the functional member prepared in the above-mentioned Examples and Comparative Examples.

<Calculation of solid acid value>
The acid values of the easy-adhesive layer coating liquid and the functional layer coating liquid of Examples 1 to 8 and Comparative Examples 1 to 6 described above were obtained by the indicator titration method specified in JIS K 2501: 2003, respectively. And the value calculated from the solid content concentration was taken as the solid content acid value. The calculation results are shown in Table 3.

<Adhesion test>
1. 1. Initial adhesion test The functional layer surface of the functional members produced in the above-mentioned Examples and Comparative Examples was tested based on the grid peeling test specified by JIS K 5400 and evaluated according to the following criteria. "◎" indicates that no peeling is observed in all of the 100 squares on the board, and "◎" indicates that no peeling is observed in 80 or more of the 100 squares. "○", the state where more than a quarter of the 100 squares did not show peeling was less than 80 squares was defined as "x". The measurement results are shown in Table 3.

2. 2. Adhesion test after high temperature and high humidity exposure The functional members produced in the above-mentioned Examples and Comparative Examples were exposed for 500 hours in an environment with a temperature of 85 ° C. and a humidity of 85% (humidification was carried out with pure water). Then, the functional layer surface was tested based on the grid peeling test specified by JIS K 5400 and evaluated according to the following criteria. "◎" indicates that no peeling is observed in all of the 100 squares on the board, and "◎" indicates that no peeling is observed in 80 or more of the 100 squares. "○", the state where more than a quarter of the 100 squares did not show peeling was less than 80 squares was defined as "x". The measurement results are shown in Table 3.

Table 3

As is clear from the results in Table 3, the functional members of Examples 1 to 8 contain a polyester-acrylic composite resin in which the composition for forming the easy-adhesion layer on the substrate contains a glycidyl group, and the composition thereof. The solid content acid value of the composition is 2.5 to 6.0 mgKOH / g, and the composition for forming the functional layer contains a compound having a functional group reactive with a glycidyl group, and the composition thereof. Since the solid acid value of the solid content was less than 4.0 mgKOH / g, both the initial adhesion test and the adhesion test after high temperature and high humidity exposure were evaluated well. The adhesion was excellent.

On the other hand, in Comparative Example 1 and Comparative Example 6, since the composition for forming the easy-adhesion layer did not contain a compound having a glycidyl group, the adhesion between the base material and the easy-adhesion layer and the adhesion between the easy-adhesion layer and the functional layer The addition reaction for developing adhesion did not occur, and the initial adhesion and the adhesion after high temperature and high humidity exposure were inferior. In Comparative Examples 1 and 4, the solid acid value of the composition for forming the easy-adhesion layer was less than 2.5 mgKOH / g, so that the addition reaction for exhibiting the adhesion did not proceed sufficiently. As a result, the initial adhesion and the adhesion after high temperature and high humidity exposure were inferior. In Comparative Example 3 and Comparative Example 5, since the solid acid value of the composition for forming the easy-adhesion layer exceeded 6.0 mgKOH / g, side reactions such as ring-opening polymerization of the glycidyl group were prioritized, and the adhesion was given priority. The addition reaction to develop the sex was inhibited, and the initial adhesion and / or the adhesion after high temperature and high humidity exposure was inferior. In Comparative Example 2, the solid acid value of the composition for forming the easy-adhesion layer was within a good range, but the solid acid value for forming the functional layer exceeded 4.0 mgKOH / g. The adhesion was inferior after high temperature and high humidity exposure because the addition reaction for developing the adhesion did not proceed sufficiently. Further, Comparative Example 1 was inferior in initial adhesion and adhesion after high temperature and high humidity exposure because the concentration of the acrylic component of the composition for forming the easy-adhesion layer was low, and Comparative Example 5 was a composition for forming the easy-adhesion layer. Since the concentration of the acrylic component in the above was too high, the adhesion was inferior after exposure to high temperature and high humidity.

10 ... base material, 20 ... easy adhesive layer, 30 ... functional layer, 40 ... backcoat layer

Claims (6)

It is a functional member in which an easy-adhesion layer and a functional layer are laminated in this order on at least one surface of a base material, and the composition for forming the easy-adhesion layer contains a polyester-acrylic composite resin having a glycidyl group. Moreover, the solid content acid value of the composition is 2.5 to 6.0 mgKOH / g, and the composition for forming the functional layer contains a compound having a functional group reactive with a glycidyl group, and the composition is said to be present. A functional member having a solid acid value of 4.0 mgKOH / g or less in the composition. The functional member according to claim 1, wherein the composition for forming the easy-adhesive layer contains the polyester-acrylic composite resin as a main component. The functional member according to claim 1 or 2, wherein the content of the acrylic resin component in the total solid content of the composition for forming the easy-adhesive layer is 20 to 50% by weight. .. The functional member according to any one of claims 1 to 3, wherein the functional group having reactivity with the glycidyl group is a hydroxy group. The aspect according to any one of claims 1 to 4, wherein the surface on which the easy-adhesion layer of the base material is laminated is one in which a functional group having reactivity with a glycidyl group is introduced by surface treatment. The functional member described. The functional member according to claim 5, wherein the functional group having reactivity with the glycidyl group introduced by the surface treatment is a hydroxy group.

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