JP2015223710A - Flexible transparent substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent substrate which can be made flexible, thin and lightweight while maintaining moisture-proof properties and gas barrier properties.SOLUTION: There is provided a flexible transparent substrate which comprises an inorganic glass film having a thickness of 10 to 100 μm, a decorative layer laminated on at least a part of a peripheral part on a first surface of the inorganic glass film and a first transparent resin layer laminated on the residual part of the first surface of the inorganic glass film. The first resin layer is composed of (a) an acrylic polymer having a weight average molecular weight of 100000 or more, (b) a compound having at least two (meth)acryloyl groups and (c1) a cured product of a composition containing a polymerization initiator, the structural unit having a nitrogen atom-containing group in the (a) component is 5 mass% or less of the entire acrylic polymer and the (a) component contains a structural unit having a functional group.

Description

  The present invention relates to a flexible transparent substrate, and more particularly to a flexible transparent substrate used for a display device, a lighting device and the like.

  The display device is a device that displays an image, such as a liquid crystal display device, a plasma display device, an organic EL (Electro Luminescence) device, or the like. A touch panel may be attached to the display surface of the display device. The illumination device is a device having a function of brightening a specific place using various light sources, such as an incandescent bulb, a fluorescent lamp, a lamp, an LED, and an organic EL device.

  In order to prevent damage, a transparent substrate using glass or plastic is often installed on the surface of the display device or the lighting device. The transparent substrate is composed of a transparent region in which an image or light emission can be visually recognized from the outside, and a non-transparent region that is shielded by a peripheral region so that it cannot be visually recognized from the outside. The peripheral area is also an area for arranging characters for indicating information such as a company name and model name, a color for decoration, a pattern, and the like. For this reason, a peripheral area | region may be called a decoration area | region.

  FIG. 5 is a schematic cross-sectional view showing an example of a conventional transparent substrate 30. The transparent substrate 30 in FIG. 5 includes an inorganic glass plate 21 as a protective cover, a decorative layer 23 that is laminated on a part of one surface thereof to form a decorative region, and the inorganic glass plate 21 and the decorative layer 23. And a transparent adhesive layer 25 formed so as to cover the whole. The transparent adhesive layer 25 is made of OCA (Optical Clear Adhesive). For example, Patent Document 1 discloses a protective plate for a portable display device using a thick glass plate for maintaining strength.

JP 2008-83263 A JP 2010-176111 A

  With the expansion of application and reduction of manufacturing costs, display devices or lighting devices are required to be flexible, thin, and light, and the same demands are increasing for members to be used. In a conventional transparent substrate, a thick inorganic glass plate exceeding 500 μm is used for the purpose of maintaining strength, and this makes it difficult to make it flexible, thin and light.

  It has been proposed to solve the above problems by coating a resin instead of the thick inorganic glass plate 21 (Patent Document 2). However, in this configuration, moisture resistance and gas barrier properties are inferior to those using an inorganic glass plate. Therefore, for example, there is a problem that it is difficult to apply to a device such as an organic EL that easily deteriorates due to moisture and oxygen, and the range of application is limited.

  An object of this invention is to provide the transparent substrate which can implement | achieve flexibility, thickness reduction, and weight reduction, maintaining moisture resistance and gas-barrier property.

  The flexible transparent substrate of the present invention includes an inorganic glass film having a thickness of 10 to 100 μm, a decorative layer laminated on at least a part of the peripheral edge of the first surface of the inorganic glass film, and a first inorganic glass film. A first transparent resin layer laminated on the remaining portion of the surface, the first transparent resin layer comprising: (a1) an acrylic polymer having a weight average molecular weight of 100,000 or more; and (b1) at least two The structural unit having a nitrogen atom-containing group in the component (a1) is a cured product of the first composition containing a compound having a (meth) acryloyl group and (c1) a polymerization initiator. The component (a1) contains a structural unit having a functional group.

  Since the flexible transparent substrate includes a resin layer excellent in transparency and a sufficiently thin inorganic glass film, the flexible transparent substrate is thin, lightweight, and flexible while having moisture resistance and gas barrier properties. The first composition may further contain (d1) an antioxidant. Thereby, coloring by the deterioration at the time of the heat | fever of a resin composition is suppressed, and transparency at the time of heat | fever can be improved.

  The flexible transparent substrate may further include a second transparent resin layer laminated on the second surface of the inorganic glass film. The second transparent resin layer comprises (a2) an acrylic polymer having a weight average molecular weight of 100,000 or more, (b2) a compound having at least two (meth) acryloyl groups, and (c2) a polymerization initiator. The structural unit having a nitrogen atom-containing group in the component (a2) is 5% by mass or less of the entire acrylic polymer, and the component (a2) has a functional group. It may contain a structural unit. The second composition may further contain (d2) an antioxidant. Thereby, coloring by the deterioration at the time of the heat | fever of a resin composition is suppressed, and transparency at the time of heat | fever can be improved.

  The first composition and the second composition may be the same as or different from each other. In the present specification, hereinafter, the components (a1) and (a2) are referred to as “(a) component”, the components (b1) and (b2) are referred to as “(b) component”, and (c1 ) Component and (c2) component are expressed as “(c) component”, and (d1) component and (d2) component are expressed as “(d) component”.

  The component (a) preferably includes a structural unit having an alicyclic structure. Thereby, since the amorphous component in an acrylic polymer increases, it exists in the tendency for transparency to become high. Further, when compared with an aliphatic structural unit having the same carbon number, the glass transition temperature (Tg) is improved and the heat resistance tends to be high.

  (A) It is preferable that the functional group in a component contains an epoxy group. (A) Adhesion to an inorganic glass film can be improved by including an epoxy group such as a glycidyl group in a part of the component.

  The surface of the decorative layer and the surface of the first transparent resin layer, which are opposite to the inorganic glass film, are preferably formed flush with each other. This eliminates the need for further laminating a resin or the like in order to flatten the surface of the transparent substrate.

  The flexible transparent substrate according to the present invention may have the following aspects. The flexible transparent substrate according to this aspect includes an inorganic glass film having a thickness of 10 to 100 μm, a decorative layer laminated on at least a part of the peripheral edge of the first surface of the inorganic glass film, and a first inorganic glass film. A first transparent resin layer laminated on the remaining portion of the surface, the first transparent resin layer comprising: (a ′) a compound having at least two ethylenically unsaturated groups; and (b ′) thermal polymerization. It consists of the hardened | cured material of the 3rd composition containing an initiator, (c ') hindered phenol type compound, (d') thioether type compound, and (e ') the compound which has a thiol group. The component (a ′) preferably contains a urethane compound having a (meth) acryloyl group.

  The flexible substrate of the above aspect may further include a second transparent resin layer laminated on the second surface opposite to the first surface of the inorganic glass film. This 2nd transparent resin layer may consist of hardened | cured material of the said 1st, 2nd or 3rd resin composition.

  In the present invention, the visible light transmittance of the first and / or second transparent resin layer is preferably 80% or more. The thickness of the decoration layer is preferably 1 to 30 μm. The thickness of the first transparent resin layer is preferably 1 to 30 μm.

  The flexible transparent substrate can be suitably used for a display device or a lighting device.

  ADVANTAGE OF THE INVENTION According to this invention, the flexible transparent substrate which can implement | achieve flexibility, thickness reduction, and weight reduction can be provided, maintaining moisture resistance and gas barrier property.

It is a schematic cross section of the flexible transparent substrate which concerns on 1st Embodiment of this invention. (A) is a top view of the flexible transparent substrate shown in FIG. 1, (b) is a top view which shows the modification. (A) And (b) is a top view which shows the modification of the flexible transparent substrate shown in FIG. 1, respectively. It is a schematic cross section of the flexible transparent substrate which concerns on 2nd Embodiment of this invention. It is a schematic cross section which shows the conventional transparent substrate.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant descriptions are omitted. For the convenience of the drawings, the dimensional ratios in the drawings do not necessarily match those described. In the present specification, “(meth) acryloyl group” means “acryloyl group” or a “methacryloyl group” corresponding thereto. The same applies to other similar expressions such as (meth) acrylate.

<Configuration of flexible transparent substrate having decorative layer>
FIG. 1 is a schematic cross-sectional view of a flexible transparent substrate 10 according to the first embodiment, and FIGS. 2 and 3 are schematic plan views showing modifications thereof. The flexible transparent substrate 10 includes a rectangular inorganic glass film 1, a decorative layer 5 laminated on the peripheral edge 1 b of the first surface 1 a of the inorganic glass film 1, and the remaining first surface 1 a of the inorganic glass film 1. The first transparent resin layer 7a laminated on the part (the part where the decorative layer 5 is not laminated) 1c is provided.

  The decorative layer 5 may be formed on the entire peripheral edge 1b of the first surface 1a (over the entire circumference) (see FIG. 2A), and is formed in an L shape along two adjacent sides. (See (b) of FIG. 2). Alternatively, the decorative layer 5 may be formed only on two opposite sides of the first surface 1a (see (a) of FIG. 3) or may be formed on three sides ((b) of FIG. 3). )reference). Although not shown, the decorative layer 5 may be formed only on one side of the first surface 1a. The decorative layer 5 can be provided in any shape on the peripheral edge 1b of the first surface 1a, and does not necessarily have to be continuous. The boundary line between the decorative layer 5 and the first transparent resin layer 7a is not limited to a rectangle (rectangle or square), and may be a circle, an ellipse, a parallelogram, a polygon, or the like. The shape of the flexible transparent substrate 10 is typically rectangular, but the shape is not particularly limited, and may be a circle, an ellipse, a parallelogram polygon, or the like.

  What is necessary is just to set the length of one side of the flexible transparent substrate 10 according to the use (for example, mobile phone terminals, such as a smart phone, a personal computer, and a television), and it can be set to 1-500cm, 3-15cm, 30- It can also be 40 cm or 220-250 cm. What is necessary is just to set the width | variety (width W in FIG. 1) of the decoration layer 5 according to the size of a flexible transparent substrate 10,20, a use, etc., and can be 0.1-50 cm, 1-3 cm or 5 -10 cm.

The total thickness of the flexible transparent substrate 10 is preferably 150 μm or less, more preferably 120 μm or less, and further preferably 50 μm to 100 μm. Even if the 1st transparent resin layer 7a is thin, it can contribute to the improvement of impact resistance and toughness. Therefore, the flexible transparent substrate 10 having the first transparent resin layer 7a is lightweight and thin, and has excellent process compatibility. Weight per unit area of the flexible transparent substrate 10 is preferably 0.2 g / cm ² or less, more preferably 0.001-0.2 grams / cm ^2, more preferably 0.01 to 0.1 g / cm ² .

  The light transmittance of the flexible transparent substrate 10 at a wavelength of 550 nm is preferably 80% or more, and more preferably 85% or more. Preferably, the flexible transparent substrate 10 has a light transmittance reduction rate of 5% or less after heat treatment at 180 ° C. for 2 hours. This is because, with such a reduction rate, a practically acceptable light transmittance can be ensured even when heat treatment necessary for the manufacturing process of the display element and the solar cell is performed.

  The surface roughness Ra of the flexible transparent substrate 10 (substantially, the surface roughness Ra of the inorganic glass film 1, the transparent resin layer 7a or other layers) is preferably 50 nm or less, more preferably 30 nm or less, and further Preferably it is 10 nm or less. The waviness of the flexible transparent substrate 10 is preferably 0.5 μm or less, and more preferably 0.1 μm or less. With the flexible transparent substrate 10 having such characteristics, even if an organic EL layer, an organic TFT layer, or the like is formed on the transparent resin layer 7a side, the same performance as when formed on glass can be obtained.

  FIG. 4 is a schematic cross-sectional view of the flexible transparent substrate 20 according to the second embodiment. The flexible transparent substrate 20 and its modification (not shown) further include a second transparent resin layer 7b laminated on the second surface 1d opposite to the first surface 1a of the inorganic glass film 1. Preferably have the same configuration, performance, physical properties, and the like as those of the above-described flexible transparent substrate 10 and modifications thereof. The total thickness of the flexible transparent substrate 20 is preferably 150 μm or less, more preferably 50 to 100 μm. The visible light transmittance of the flexible transparent substrate 20 is preferably 80% or more.

  Hereafter, each structure of the transparent substrate in the above-mentioned embodiment is demonstrated in detail.

<Inorganic glass film>
Any suitable inorganic glass film 1 may be employed as long as it is in the form of a film. The inorganic glass film 1 includes, for example, soda lime glass, borate glass, aluminosilicate glass, quartz glass, and the like according to the classification according to the composition. Moreover, according to the classification | category by an alkali component, an alkali free glass, low alkali glass, etc. are mentioned. The content of the alkali metal component of the inorganic glass film 1 _{(e.g., Na 2 O, K 2 O} , Li 2 O) is preferably 15 wt% or less, and more preferably not more than 10 wt%.

  The thickness of the inorganic glass film 1 is 10-100 micrometers, More preferably, it is 10 micrometers-80 micrometers, More preferably, it is 20 micrometers-70 micrometers. The flexible transparent substrate 10 includes a transparent resin layer 7a on the surface 1a, and the flexible transparent substrate 20 includes a transparent resin layer 7a on the surface 1a and a transparent resin layer 7b on the surface 1d. For this reason, the thickness of the inorganic glass film 1 can be made much thinner than before. Thereby, the flexible transparent substrates 10 and 20 can be made thin, lightweight, and flexible.

  The total light transmittance of the inorganic glass film 1 is preferably 90% or more. The light transmittance at a wavelength of 550 nm is preferably 85% or more. The refractive index of the inorganic glass film 1 at a wavelength of 550 nm is preferably 1.4 to 1.65.

The density of the inorganic glass film 1 is preferably ^{2.3g / cm 3 ~3.0g / cm 3} , more preferably from ^{2.3g / cm 3 ~2.7g / cm 3} . If it is thin inorganic glass of the said range, the flexible transparent substrate reduced in weight will be obtained.

  Arbitrary appropriate methods may be employ | adopted for the shaping | molding method of the inorganic glass film 1. FIG. Typically, the inorganic glass film 1 is a mixture of a main raw material such as silica or alumina, an antifoaming agent such as sodium nitrate or antimony oxide, and a reducing agent such as carbon at a temperature of 1400 ° C to 1600 ° C. It is produced by melting and forming into a thin plate shape and then cooling. Examples of the thin plate forming method for the inorganic glass film 1 include a slot down draw method, a fusion method, and a float method. The inorganic glass formed into a film shape by these methods may be chemically polished with a solvent such as hydrofluoric acid, if necessary, in order to reduce the thickness or improve the smoothness.

  As the inorganic glass film 1, a commercially available one may be used as it is, or a commercially available inorganic glass may be used after being polished to have a desired thickness. Examples of commercially available inorganic glass films include “7059”, “1737” or “EAGLE 2000” manufactured by Corning, “AN100” manufactured by Asahi Glass, “NA-35” manufactured by NH Techno Glass, and “OA” manufactured by Nippon Electric Glass. -10 "," D263 "or" AF45 "manufactured by Schott Corporation.

<Decoration layer>
The decoration layer 5 is a layer for writing a decoration pattern, characters, numbers, patterns, and the like on the peripheral edge (decoration region) of the flexible transparent substrate 10. The thickness of the decoration layer 5 becomes like this. Preferably it is 1-30 micrometers, More preferably, it is 5-20 micrometers. It is preferable that the surface of the decorating layer 5 opposite to the inorganic glass film 1 and the surface of the first transparent resin layer 7a opposite to the inorganic glass film 1 are formed flush with each other (see FIG. 1). Since these are formed flush, there is an advantage that it is not necessary to further provide a resin layer such as OCA (optical transparent adhesive) in order to fill the step. By making the thickness of the decoration layer 5 equal to the thickness of the first transparent resin layer 7a, these can be made flush.

  The decorative layer 5 is formed of a resin containing a colored paint. The decorative layer 5 is decorated on the first surface 1a of the inorganic glass film 1 by, for example, screen printing, gravure printing, other appropriate printing, or sublimation (thermal) transfer or foil press transfer (so-called hot stamp). Can be obtained by forming The decorative layer 5 can be formed in an arbitrary color such as black, white, pink, or the like. In addition, a desired logo such as letters, numbers, and patterns can be formed in an arbitrary region of the decorative layer 5 by foil stamping transfer (so-called hot stamping). The decorative layer 5 may be a single layer (that is, one layer) or a plurality of layers. When there is no pattern in the decorative layer 5 or when the pattern is simple, it is preferable that the printed layer pattern is a single layer. Moreover, when the decoration layer 5 has multiple colors or a complicated pattern, it is preferable to make the decoration layer 5 into multiple layers. Diversification of decoration can be realized by multilayering the decoration layer 5.

<Transparent resin layer>
The 1st transparent resin layer 7a is laminated | stacked on the part 1c which is the 1st surface 1a of the inorganic glass film 1, and the decoration layer 5 is not laminated | stacked (refer FIG. 1). In order to make the surface of the first transparent resin layer 7a and the surface of the decorative layer 5 flush with each other, the thickness of the first transparent resin layer 7a is preferably the same as that of the decorative layer 5. That is, the thickness of the 1st transparent resin layer 7a becomes like this. Preferably it is 1-30 micrometers, More preferably, it is 5-20 micrometers.

  The transparent resin layer 7b is laminated on the second surface 1d of the inorganic glass film 1 (see FIG. 4). The thickness of the transparent resin layer 7b is preferably 1 μm to 500 μm, more preferably 5 μm to 70 μm, and still more preferably 10 μm to 50 μm. The thickness of the transparent resin layer 7a and the thickness of the transparent resin layer 7b may be the same or different. Preferably, the transparent resin layers 7a and 7b have the same thickness. Furthermore, the transparent resin layers 7a and 7b may be made of the same resin or a resin having the same characteristics, or may be made of different resins. Preferably, the transparent resin layers 7a and 7b are made of the same resin. Therefore, most preferably, each resin cured material layer is comprised so that it may become the same thickness with the same resin. If it is such a structure, even if it heat-processes, since a thermal stress is equally applied to both surfaces of inorganic glass, curvature or a wave | undulation will become difficult to produce very much.

  The total thickness of the transparent resin layers 7a and 7b is preferably 0.01 to 6, more preferably 0.05 to 3, and still more preferably 0.00 relative to the thickness of the inorganic glass film 1. 1 to 1.5. When the total thickness of the transparent resin layers 7a and 7b is within such a range, the flexible transparent substrates 10 and 20 having excellent flexibility and dimensional stability can be obtained.

  The total light transmittance of the transparent resin layers 7a and 7b is preferably 80% or more. The visible light transmittance of the transparent resin layers 7a and 7b is preferably 80% or more. Moreover, it is desirable to comprise from an acrylic compound. The 5% thermal weight loss temperature of the cured resin in the transparent resin layers 7a and 7b is preferably 150 ° C. or more. The total light transmittance and the 5% thermal weight loss temperature can be measured by, for example, the methods described in Examples.

  The transparent resin layers 7a and 7b are composed of the following first resin composition (corresponding to the above-mentioned “first composition” and “second composition”) or the second resin composition (described above “third”. It can be obtained by curing.

<First resin composition>
The first resin composition contains (a) an acrylic polymer having a weight average molecular weight of 100,000 or more, (b) a compound having at least two (meth) acryloyl groups, and (c) a polymerization initiator. . In addition, the structural unit which has a nitrogen atom containing group in (a) component is 5 mass% or less of the whole acrylic polymer, and (a) component contains the structural unit which has a functional group. This will be specifically described below.

(A) Acrylic polymer having a weight average molecular weight of 100,000 or more The acrylic polymer used in this embodiment is a polymer obtained by polymerizing one acrylic monomer having one (meth) acryloyl group in the molecule, or 2 It refers to those copolymerized by combining more than one species. As long as the effect of the present invention is not impaired, a compound having two or more (meth) acryloyl groups in the molecule, or a polymerizable compound having no (meth) acryloyl group (acrylonitrile, styrene, vinyl acetate) , A compound having one polymerizable unsaturated bond in the molecule such as ethylene and propylene, and a compound having two or more polymerizable unsaturated bonds in the molecule such as divinylbenzene) copolymerized with an acrylic monomer. There may be. From such a viewpoint, the acrylic polymer used in the present embodiment has 30 to 100% by mass of an acrylic monomer having one (meth) acryloyl group in the molecule based on the total amount of the acrylic polymer. And preferably 50 to 100% by mass.

  The acrylic polymer having a weight average molecular weight of 100,000 or more according to this embodiment includes a structural unit having a functional group.

  The method for introducing the functional group into the acrylic polymer is not particularly limited, but the functional group-containing monomer having a functional group is not limited to suspension polymerization, which is also called bead polymerization, granular polymerization, pearl polymerization, or the like, but is also solution polymerization or bulk polymerization. The functional group can be introduced into the acrylic polymer by random copolymerization by an existing method such as precipitation polymerization or emulsion polymerization. Among these, it is preferable to apply the suspension polymerization method from the viewpoint of high molecular weight at low cost.

  Suspension polymerization is performed by adding a suspending agent in an aqueous solvent. Examples of the suspending agent include water-soluble polymers such as polyvinyl alcohol, methylcellulose, and polyacrylamide, and poorly soluble inorganic substances such as calcium phosphate and magnesium pyrophosphate. Among them, nonionic water-soluble polymers such as polyvinyl alcohol are preferable. When a nonionic water-soluble polymer is used, it is preferable in that the possibility that ionic impurities remain in the obtained acrylic copolymer is low. The water-soluble polymer is preferably used in an amount of 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of monomers.

  Moreover, in a polymerization reaction, you may use the polymerization initiator generally used, a chain transfer agent, etc. As a polymerization initiator, the same thing as the (c) polymerization initiator mentioned later is mentioned. Examples of the chain transfer agent include thiols such as n-octyl mercaptan.

  The functional group-containing monomer has at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group, an amide group, a phosphoric acid group, a cyano group, a maleimide group, and an epoxy group in the molecule. It preferably has a group and at least one polymerizable carbon-carbon double bond.

  As functional group-containing monomers, carboxyl group-containing monomers such as (meth) acrylic acid and itaconic acid, acid anhydride group-containing monomers such as maleic anhydride, (meth) acrylic acid-2-hydroxymethyl, Hydroxyl-containing single monomers such as (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, N-methylol (meth) acrylamide, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene Body, amino group-containing monomers such as diethylaminoethyl (meth) acrylate, phosphate group-containing monomers such as 2- (meth) acryloyloxyethyl acid phosphate, vinyl cyanide compounds such as (meth) acrylonitrile, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Ni-propylmaleimide N-substituted maleimides such as N-butylmaleimide, N-butylmaleimide, Nt-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, (meta ) Glycidyl acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) Acrylic acid-6,7-epoxyheptyl, (meth) acrylic acid-3-methyl-3,4-epoxybutyl, (meth) acrylic acid-4-methyl-4,5-epoxypentyl, (meth) acrylic acid- 5-methyl-5,6-epoxyhexyl, (meth) acrylic acid-β-methylglycidyl, α-ethyl acetate Epoxy group-containing monomers such as β-methylglycidyl silylate can be used. These can be used alone or in combination of two or more.

  Among these, it is particularly preferable to use an epoxy group-containing monomer such as glycidyl (meth) acrylate. Furthermore, for example, the glycidyl group-containing (meth) acrylic polymer obtained by using such a monomer is preferably compatible with the acrylic monomer or oligomer. The glycidyl group-containing (meth) acrylic polymer may be synthesized by a conventional method, or a commercially available product may be obtained. As a commercial item, HTR-860P-3 (Nagase ChemteX Corporation, a brand name) etc. are mentioned.

  The amount of the structural unit having the functional group is preferably 0.5 to 6.0% by mass, more preferably 0.5 to 5.0% by mass, and still more preferably based on the total amount of the acrylic polymer. Is 0.8-5.0 mass%. When the amount of the structural unit having a functional group is within this range, it is possible to secure adhesive force and to prevent gelation.

  Further, in the acrylic polymer having a weight average molecular weight of 100,000 or more according to the present embodiment, the structural unit having a nitrogen atom-containing group is preferably 5% by mass or less, more preferably 3% by mass based on the entire acrylic polymer. It is below, More preferably, it is 1 mass% or less, and it is especially preferable not to contain the structural unit which has a nitrogen atom containing group. Examples of the nitrogen atom-containing group include an amino group, an amide group, a cyano group, and a maleimide group. Examples of the structural unit having a nitrogen atom-containing group include structural units derived from monomers containing a nitrogen atom among the functional group-containing monomers listed above, and vinyl cyanide such as (meth) acrylonitrile. Compounds.

Examples of monomers other than the functional group-containing monomer used when synthesizing the acrylic polymer according to the present embodiment include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylate n-. Propyl, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic acid n-hexyl, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, butoxyethyl (meth) acrylate, phenyl (meth) acrylate , (Meth) acrylic acid esters such as benzyl (meth) acrylate and naphthyl (meth) acrylate, α-methylstyrene, α-ethyls Tylene, α-fluorostyrene, α-chlorostyrene, α-bromostyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene, methoxystyrene, styrene and other aromatic vinyl compounds, (meth) acrylic acid cyclopentyl, (meth) Cyclohexyl acrylate, methyl cyclohexyl (meth) acrylate, trimethylhexyl (meth) acrylate, norbornyl (meth) acrylate, norbornyl methyl (meth) acrylate, phenyl norbornyl (meth) acrylate, (meth) Isobornyl acrylate, bornyl (meth) acrylate, menthyl (meth) acrylate, fentil (meth) acrylate, adamantyl (meth) acrylate, tricyclo (meth) acrylate [5.2.1.0 ^2,6 ] Dec-8-yl, (meta Acrylic acid tricyclo [5.2.1.0 ^{2, 6]} deca-4-methyl, include alicyclic monomers such as (meth) cyclodecyl acrylate. These can be used alone or in combination of two or more.

  Among these, (meth) acrylic acid esters are preferably used because they easily synthesize the component (a) having a weight average molecular weight of 100,000 or more without gelation. Among (meth) acrylic acid esters, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are excellent in copolymerizability with a functional group-containing monomer. Further preferred.

［式（１）中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は脂環式基又は複素環式基を示し、Ｘは炭素数１〜６のアルキレン基を示し、ｎは０〜１０の整数を示す。ｎが２以上の整数であるとき、複数存在するＸは互いに同一であっても異なっていてもよい。ここで脂環式基とは、炭素原子が環状に結合した構造を有する基であり、複素環式基とは、炭素原子及び１以上のヘテロ原子が環状に結合した構造を有する基である。］ The component (a) preferably contains a structural unit having an alicyclic or heterocyclic structure. Examples of the alicyclic or heterocyclic structure-containing monomer used in producing an acrylic polymer containing a structural unit having an alicyclic or heterocyclic structure are represented by the following general formula (1). Can be mentioned.

[In Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alicyclic group or a heterocyclic group, X represents an alkylene group having 1 to 6 carbon atoms, and n represents 0 to 0. An integer of 10 is shown. When n is an integer of 2 or more, a plurality of Xs may be the same or different from each other. Here, an alicyclic group is a group having a structure in which carbon atoms are bonded in a ring, and a heterocyclic group is a group having a structure in which a carbon atom and one or more heteroatoms are bonded in a ring. ]

［式（２）中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０はそれぞれ独立に、水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^１１は水素原子、炭素数１〜４のアルキル基、又はＯＲ^１２で示される構造を示し、Ｒ^１２は水素原子又は炭素数１〜８のアルキル基を示す。］ The R ^2, for example, those represented by the following formula (2).

[In the formula (2), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; ¹¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a structure represented by OR ¹² , and R ¹² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

Examples of the compound represented by the general formula (1) include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate.

  The content of monomers other than these functional group-containing monomers is not particularly limited, but the Tg of the component (a) used in the resin composition according to this embodiment is in the range of −50 to 50 ° C. For example, as a monomer, glycidyl methacrylate is 2.5% by mass, methyl methacrylate is 43.5% by mass, ethyl acrylate is 18.5% by mass, and butyl acrylate. By using 35.5% by mass, the component (a) which is an epoxy group-containing acrylic polymer having a Tg of 12 ° C. and a weight average molecular weight of 100,000 or more can be synthesized.

  The mixing ratio when the functional group-containing monomers are used in combination is determined in consideration of the Tg of the acrylic polymer, and the Tg is preferably −50 ° C. or higher. This is because when the Tg is −50 ° C. or higher, the tackiness of the resin composition in the B-stage state is appropriate, and no problem is caused in handleability. From such a viewpoint, the mixing ratio of the functional group-containing monomer and the monomer other than the functional group-containing monomer is preferably 100: 0 to 0.1: 99.9, and 100: 0 More preferably, it is 1:99.

  When the above monomer is polymerized to produce an acrylic polymer having a weight average molecular weight containing a functional unit-containing structural unit of 100,000 or more, the polymerization method is not particularly limited, and pearl polymerization, solution polymerization, Methods such as suspension polymerization can be used.

The weight average molecular weight of the acrylic polymer according to this embodiment is preferably 120,000 to 3 million, and more preferably 120,000 to 2 million. When the weight average molecular weight is within this range, the strength, flexibility, and tackiness when sheet-like or film-like are appropriate, and the circuit filling property of the wiring can be ensured because the flow property is appropriate. In the present embodiment, the weight average molecular weight is, for example, a value measured by gel permeation chromatography (GPC) under the following conditions and converted using a standard polystyrene calibration curve. The calibration curve can be approximated by a cubic equation using a standard polystyrene kit PStQuick series C (Tosoh Corporation, trade name).
Pump: L6000 Pump (Hitachi, Ltd.)
Detector: L3300 RI Monitor (Hitachi, Ltd.)
Column: Gelpack GL-S300MDT-5 (two in total) (Hitachi Chemical Co., Ltd., trade name)
Column size: Diameter 8mm x 300mm
Eluent: DMF / THF (mass ratio 1/1) + LiBr · H ₂ O 0.03 mol / l + H ₃ PO ₄ 0.06 mol / l
Sample concentration: 0.1% by mass
Flow rate: 1 ml / min
Measurement temperature: 40 ° C

  The amount of the acrylic polymer component having a weight average molecular weight including a structural unit having a functional group of 100,000 or more is 10 to 10 parts by mass based on 100 parts by mass of the following compound (b) having at least two (meth) acryloyl groups. 400 parts by weight is preferred. When it is within this range, a good storage elastic modulus is exhibited, flowability during molding can be suppressed, and handleability at high temperatures can be sufficiently obtained. From such a viewpoint, the amount used is more preferably 15 to 350 parts by mass, and particularly preferably 20 to 300 parts by mass.

(B) Compound having at least two (meth) acryloyl groups The compound having at least two (meth) acryloyl groups according to this embodiment is not particularly limited and is a polyfunctional (meth) acryl having an alicyclic skeleton. Monomers, polyfunctional (meth) acrylic monomers having an aliphatic skeleton, polyfunctional (meth) acrylic monomers having a dioxane glycol skeleton, polyfunctional (meth) acrylic monomers having a functional group, etc. It is done. Here, “polyfunctional” refers to a (meth) acryloyl group, and means that the compound has at least two (meth) acryloyl groups.

  From the viewpoint of improving the transparency of the cured product, a polyfunctional (meth) acrylic monomer having an alicyclic skeleton and a polyfunctional (meth) acrylic monomer having a dioxane glycol skeleton are preferable.

  As a polyfunctional (meth) acryl monomer, the following (meth) acryl monomer which has two (meth) acryloyl groups can be mentioned.

  Examples of the (meth) acrylic monomer having two (meth) acryloyl groups include cyclohexane-1,4-dimethanol di (meth) acrylate, cyclohexane-1,3-dimethanol di (meth) acrylate, tricyclodecane dimethylol di ( (Meth) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-684, tricyclodecane dimethylol diacrylate, etc.), tricyclodecane dimethanol di (meth) acrylate (for example, Shin-Nakamura Chemical Co., Ltd., A-DCP, Tricyclodecane dimethanol diacrylate, etc.), dioxane glycol di (meth) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-604, dioxane glycol diacrylate, Shin-Nakamura Chemical Co., Ltd., A-DOG, dioxane glycol di) Acrylate, etc.), neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene oxide modified 1,6-hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, (poly) ethylene oxide modified neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate (preferably polyethylene oxide modified bisphenol A type di (meth) acrylate, more preferably ethyl Emissions oxide 5-15 mol-modified bisphenol A Kataji (meth) acrylate), and (poly) ethylene oxide-modified phosphoric acid di (meth) acrylate.

  Among these, dioxane glycol diacrylate, tricyclodecane dimethanol diacrylate, and the like are more preferable from the viewpoint of improving the transparency of the cured product.

  In addition, as the polyfunctional (meth) acrylic monomer, a (meth) acrylic monomer having three (meth) acryloyl groups such as pentaerythritol tri (meth) acrylate and ethylene oxide-modified isocyanuric acid tri (meth) acrylate Can also be mentioned. In addition, the resin composition which concerns on this embodiment may contain a monofunctional (meth) acryl monomer separately from (b) component. Examples of the monofunctional (meth) acrylic monomer include the acrylic monomers exemplified for the component (a).

(C) Polymerization initiator As the (c) polymerization initiator according to this embodiment, for example, (c-1) a thermal polymerization initiator, (c-2) a photopolymerization initiator, or both can be used. .

  (C-1) As the thermal polymerization initiator, t-hexyl peroxypivalate (perhexyl PV, trade name: 1 hour half-life temperature 71.3 ° C., 10 hour half-life temperature 53.2 ° C.), dilauroyl par Oxide (Perhexyl L, trade name; 1 hour half-life temperature 79.3 ° C., 10 hour half-life temperature 61.6 ° C.), di (3,5,5-trimethylhexanoyl) peroxide (Perroyl 355, trade name; 1 hour half-life temperature 76.8 ° C., 10 hour half-life temperature 59.4 ° C., 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, trade name; 1 hour Half-life temperature 84.4 ° C., 10-hour half-life temperature 65.3 ° C., t-butyl peroxy-2-ethylhexanoate (Perbutyl O, trade name; 1-hour half-life temperature 92.1 ° C., 10 hours Deterioration temperature 72.1 ° C), benzoyl peroxide + water (Nyper BW, trade name; 1 hour half-life temperature 92.0 ° C, 10 hour half-life temperature 73.6 ° C), 1,1-di (t- Hexylperoxy) -3,3,5-trimethylcyclohexane (Perhexa TMH, trade name; 1 hour half-life temperature 106.4 ° C., 10 hour half-life temperature 86.7 ° C.), 1,1-di (t-hexyl) Peroxy) cyclohexane (Perhexa HC, trade name; 1 hour half-life temperature 107.3 ° C., 10 hour half-life temperature 87.1 ° C.), t-hexyl peroxyisopropyl monocarbonate (Perhexyl I, trade name; 1 hour) Half-life temperature 114.6 ° C., 10-hour half-life temperature 95.0 ° C., t-butyl peroxyisopropyl monocarbonate (Perbutyl I, trade name; 1-hour half-life temperature 1) 8.4 ° C., 10-hour half-life temperature 98.7 ° C.), dicumyl peroxide (Park Mill D, trade name; 1-hour half-life temperature 135.7 ° C., 10-hour half-life temperature 116.4 ° C.), n− Organic peroxides such as butyl 4,4-bis (t-butylperoxy) valerate (Perhexa V, trade name: 1 hour half-life temperature 126.5 ° C., 10 hour half-life temperature 104.5 ° C.), 2, 2′-azobisisobutyronitrile, 1,1 ′-(cyclohexane-1,1-carbonitrile) -2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (2 , 4-dimethylvaleronitrile) and the like.

  These thermal polymerization initiators can be used singly or in combination of two or more.

  Among these thermal polymerization initiators, an organic peroxide is preferable from the viewpoint that the effect of improving the physical properties of the cured product is large, and an organic peroxide having a 10-hour half-life temperature of 90 to 150 ° C. is more preferable. preferable.

  The compounding amount of the component (c-1) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). More preferably, it is 0.5-10 mass parts.

  Among the above-mentioned thermal polymerization initiators, suitable organic peroxides include dicumyl peroxide (Parkmill D) and n-butyl 4,4-bis (t-butylperoxy) valerate (Perhexa V). It is done.

  (C-2) As photopolymerization initiators, acylphosphine oxides, oxime esters, aromatic ketones, quinones, benzoin ether compounds, benzyl derivatives, 2,4,5-triarylimidazole dimers, acridine derivatives , Coumarin compounds, N-phenylglycine derivatives, and the like. In addition, the photoinitiator (c-2) used by this embodiment may be synthesize | combined by a conventional method, and a commercially available thing may be obtained.

  Among these, acylphosphine oxide and oxime esters are preferable from the viewpoints of improvement of photocurability, high sensitivity, and transparency of the cured film.

  In addition, a photoinitiator (c-2) can be used individually by 1 type or in combination of 2 or more types.

  Examples of the acylphosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE-819, BASF, trade name), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (LUCIRIN). TPO, BASF, trade name) and the like.

  Examples of oxime esters include 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyloxime)] (IRGACURE-OXE01, BASF Corporation, trade name), 1- [9-ethyl -6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (IRGACURE-OXE02, trade name of BASF), 1-phenyl-1,2-propanedione -2- [o- (ethoxycarbonyl) oxime] (Quantacure-PDO, Nippon Kayaku Co., Ltd., trade name) and the like.

  Aromatic ketones include benzophenone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N, N ′, N′-tetraethyl-4,4′-diamino. Benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE-651, BASF, trade name), 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one (IRGACURE-369, BASF, trade name), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- ON (IRGACURE-907, BASF Corporation, product name), 2-hydroxy-1- {4- [4- (2-hydroxy-2 Methyl - propionyl) - benzyl] phenyl} -2-methyl - propan-1-one (IRGACURE-127, BASF Corp., and a trade name).

  As quinones, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, Examples include 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone.

  Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether.

  Examples of the benzyl derivative include benzyl dimethyl ketal in addition to benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin.

  As 2,4,5-triarylimidazole dimer, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like. As 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazole -2-yl] -4,5-diphenylimidazole and the like.

  Examples of the acridine derivative include 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane and the like.

  Examples of coumarin compounds include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, and 7-ethylamino-4. -Methylcoumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6 -Diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-diethyl- 7-dimethylaminocoumarin, 2,3,6,7,10,11-hexanehydro-1H, 5 -Cyclopenta [3,4] [1] benzopyrano- [6,7,8-ij] quinolizine 12 (9H) -one, 7-diethylamino-5 ', 7'-dimethoxy-3,3'-carbonylbiscoumarin, 3,3′-carbonylbis [7- (diethylamino) coumarin], 7-diethylamino-3-thienoxysilkine and the like can be mentioned.

  N-phenylglycine derivatives include N-phenylglycine, N-phenylglycine butyl ester, Np-methylphenylglycine, Np-methylphenylglycine methyl ester, N- (2,4-dimethylphenyl) glycine, N-methoxyphenylglycine etc. are mentioned.

  (C-2) The blending amount of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts per 100 parts by mass of the total amount of the components (a) and (b). Part by mass, more preferably 0.75 to 5 parts by mass.

(Organic solvent)
In addition to the components (a), (b) and (c), the resin composition according to the present embodiment can be made into a varnish by dissolving or dispersing optional components described below in an organic solvent as necessary. . Thereby, the applicability | paintability to a base material can be improved and workability | operativity can be made favorable.

  There is no restriction | limiting as an organic solvent used in order to make it into a varnish form, if a component used as a resin composition can be stirred and mixed, melt | dissolved, knead | mixed or disperse | distributed uniformly, A conventionally well-known thing can be used. The organic solvent to be used is not particularly limited, and examples thereof include alcohols, ethers, ketones, amides, aromatic hydrocarbons, esters, and nitriles. Specifically, considering low-temperature volatility, etc., low boiling point diethyl ether, acetone, methanol, tetrahydrofuran, hexane, ethyl acetate, ethanol, methyl ethyl ketone, 2-propanol, etc. High boiling point toluene, methyl isobutyl ketone, 1-butanol, 2-methoxyethanol, 2-ethoxyethanol, xylene, N, N-dimethylacetamide, N, N-dimethylformamide, cyclohexanone, dimethylacetamide, butyl cellosolve, dimethyl Examples thereof include sulfoxide, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, and γ-butyrolactone. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

  Among these, it is preferable to use methyl ethyl ketone, cyclohexanone, or the like because of excellent solubility and fast drying speed.

  The amount of the organic solvent used in the resin composition according to the present embodiment is determined by the viscosity when the varnish is used, and is not particularly limited. It is used in the range of 5 to 95% by mass, more preferably 10 to 90% by mass.

(D) Antioxidant An antioxidant may be added to the resin composition according to the present embodiment as necessary. Examples of the antioxidant used in the present embodiment include phenol-based antioxidants and thioether-based antioxidants.

  The amount of the antioxidant used in the resin composition according to this embodiment is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (a), (b) and (c). preferable.

(Coupling agent)
A coupling agent can be added to the resin composition according to the present embodiment. The coupling agent used is not particularly limited, and various types such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, and a zircoaluminate coupling agent are used. .

  Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyl-tris (2-methoxyethoxy) ) Silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, methyltri (methacryloxyethoxy) silane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (N-bi Rubenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, 3- (4,5-dihydroimidazolyl) propyl Triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiisopropeno Xysilane, methyltriglycidoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate Sulfonate, phenyl triisocyanate, tetraisocyanate silane, methyl triisocyanate, vinylsilyl triisocyanate, and ethoxysilane triisocyanate and the like.

  Titanate coupling agents include isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, Isopropyldimethacrylisostearoyl titanate, isopropyl (dioctyl phosphate) titanate DOO, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the aluminum coupling agent include acetoalkoxy aluminum diisopropionate.

  Examples of the zirconate coupling agent include tetrapropyl zirconate, tetrabutyl zirconate, tetra (triethanolamine) zirconate, tetraisopropyl zirconate, zirconium acetylacetonate acetylacetone zirconium butyrate, and zirconium stearate butyrate.

（式（３）中、Ｒはカルボキシル基又はアミノ基を示す。） Examples of the zircoaluminate coupling agent include compounds represented by the following general formula (3).

(In formula (3), R represents a carboxyl group or an amino group.)

  Examples of the compound in which R is a carboxyl group include Mansheim CPG-carboxyzircoaluminate, and examples of the compound in which R is an amino group include Mansheim APO-X-aminozircoaluminate solution. Available from Rhône Poulenc.

  The blending amount of the coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the components (a), (b) and (c). is there. If this blending ratio is 0.1 parts by mass or more, the adhesive strength improving effect tends to be easily obtained, and if it is 20 parts by mass or less, the volatile content is small, and voids tend not to occur in the cured product. There is.

  Among these coupling agents, it is preferable to select a silane coupling agent that is highly effective in terms of improving the bonding or wettability of the interface between the materials.

(filler)
The resin composition according to the present embodiment may further contain a filler as necessary. Examples of the filler include inorganic fillers and organic fillers, and inorganic fillers are preferable from the viewpoint of improving heat resistance or thermal conductivity, or adjusting melt viscosity or imparting thixotropic properties.

  The inorganic filler is not particularly limited, and includes aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, titanium oxide, zirconium oxide, Examples thereof include cerium oxide, zinc oxide, aluminum borate whisker, boron nitride, crystalline silica, amorphous silica, and antimony oxide. These can be used alone or in combination of two or more.

  In order to improve thermal conductivity, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, amorphous silica and the like are preferable. For adjusting melt viscosity or imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystalline silica, amorphous Silica etc. are preferable.

  From the viewpoint of transparency and workability, the blending amount of the filler is preferably 3% by mass or less of the entire resin composition excluding the solvent.

  In the production of the varnish when the filler is added to the resin composition according to the present embodiment, in consideration of dispersibility, a physical shearing force is applied by a reiki machine, a three roll, a ball mill, a bead mill, etc. It is preferable to use after sufficiently dispersing so that there is no next aggregated particle. The above dispersion methods can be used in combination.

  Further, the mixing time can be shortened by mixing the filler and the low molecular weight material in advance and then blending the high molecular weight material.

  There is no particular limitation on the method of stirring and mixing each component uniformly, but rotation and revolution of a dissolver, static mixer, homogenizer, ultrasonic homogenizer, paint shaker, ball mill, planetary mixer, mix rotor, universal agitator, etc. In addition to the type stirrer, a method using a laika machine, a kneading apparatus such as a three-roller, and the like can be mentioned, and these can be used in combination as appropriate. After the varnish is formed, it is preferable to remove bubbles in the varnish. In this sense, the rotation and revolution type stirrer is preferably used because it can simultaneously perform mixing and dissolution and removal of bubbles.

  The resin composition according to the present embodiment may further include a moisture absorbent such as calcium oxide and magnesium oxide, a fluorosurfactant, a nonionic surfactant, a wetting improver such as a higher fatty acid, silicone oil, and the like as necessary. An anti-foaming agent, an ion trapping agent such as an inorganic ion exchanger, or the like can be added as appropriate, alone or in combination.

  In the entire resin composition excluding the solvent according to this embodiment, the nitrogen content is preferably 8% by mass or less, more preferably 5% by mass or less. By setting the nitrogen content in this range, it is preferable because coloring derived from nitrogen oxides can be further suppressed.

<Second resin composition>
The second resin composition comprises (a ′) a compound having at least two ethylenically unsaturated groups, (b ′) a thermal polymerization initiator, (c ′) a hindered phenol compound, and (d ′) a thioether compound. And (e ′) a compound having a thiol group. Moreover, the resin composition of 2nd Embodiment may further contain the above-mentioned (a) acrylic polymer whose weight average molecular weight is 100,000 or more. This will be specifically described below.

(A ′) Compound having at least two ethylenically unsaturated groups The compound having at least two ethylenically unsaturated groups used in the present embodiment is preferably a compound having at least two (meth) acryloyl groups. . The compound having at least two ethylenically unsaturated groups has a polyfunctional (meth) acrylic monomer having an alicyclic skeleton, a polyfunctional (meth) acrylic monomer having an aliphatic skeleton, and a dioxane glycol skeleton. A polyfunctional (meth) acrylic monomer, a polyfunctional (meth) acrylic monomer having a functional group, and the like can be given. Here, “polyfunctional” refers to an ethylenically unsaturated group, and means that the compound has at least two ethylenically unsaturated groups.

  From the viewpoint of improving the transparency of the cured product, a polyfunctional (meth) acrylic monomer having an alicyclic skeleton and a polyfunctional (meth) acrylic monomer having a dioxane glycol skeleton are preferable.

  As a polyfunctional (meth) acryl monomer, the following (meth) acryl monomer which has two (meth) acryloyl groups can be mentioned.

  Examples of the (meth) acrylic monomer having two (meth) acryloyl groups include cyclohexane-1,4-dimethanol di (meth) acrylate, cyclohexane-1,3-dimethanol di (meth) acrylate, tricyclodecane dimethylol di ( (Meth) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-684, tricyclodecane dimethylol diacrylate, etc.), tricyclodecane dimethanol di (meth) acrylate (for example, Shin-Nakamura Chemical Co., Ltd., A-DCP, Tricyclodecane dimethanol diacrylate, etc.), dioxane glycol di (meth) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-604, dioxane glycol diacrylate, Shin-Nakamura Chemical Co., Ltd., A-DOG, dioxane glycol di) Acrylate, etc.), neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene oxide modified 1,6-hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, (poly) ethylene oxide modified neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate (preferably polyethylene oxide modified bisphenol A type di (meth) acrylate, more preferably ethyl Emissions oxide 5-15 mol-modified bisphenol A Kataji (meth) acrylate), and (poly) ethylene oxide-modified phosphoric acid di (meth) acrylate.

  Among these, dioxane glycol diacrylate, tricyclodecane dimethanol diacrylate, and the like are more preferable from the viewpoint of improving the transparency of the cured product.

  In addition, as the polyfunctional (meth) acrylic monomer, a (meth) acrylic monomer having three (meth) acryloyl groups such as pentaerythritol tri (meth) acrylate and ethylene oxide-modified isocyanuric acid tri (meth) acrylate Can also be mentioned.

  Furthermore, the polyfunctional (meth) acrylic monomer includes, for example, a (meth) acrylate compound having an amide bond, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, a bisphenol A-based (meta ) A compound obtained by reacting an acrylate compound or a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, and a (meth) acrylic acid alkyl ester copolymer having an ethylenically unsaturated group. These can be used individually by 1 type or in combination of 2 or more types.

  The compound having at least two ethylenically unsaturated groups is preferably a urethane compound having a (meth) acryloyl group from the viewpoint of high reactivity.

  The urethane compound having a (meth) acryloyl group is, for example, a urethane (meth) acrylate or ethylene oxide (EO) modified urethane di () which is an addition reaction product of a (meth) acrylic monomer having a hydroxyl group at the β-position and the like and a diisocyanate compound. (Meth) acrylate, propylene oxide (PO) modified urethane di (meth) acrylate, EO / PO modified urethane di (meth) acrylate, urethane (meth) acrylate having carboxyl group, diol compound and two hydroxyl groups and two ethylenically unsaturated groups And at least one selected from the group consisting of a reaction product of a bifunctional epoxy (meth) acrylate having a polyisocyanate and a polyisocyanate.

  The (meth) acrylic monomer having a hydroxyl group at the β-position or the like is, for example, at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, dipentaerythritol penta (meth) acrylate and pentaerythritol tri (meth) acrylate. Species are mentioned. Examples of the diisocyanate compound include at least one selected from the group consisting of isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate.

  In order to achieve the effect of the present invention at a higher level, it is preferable to optimize the number of functional groups (number of (meth) acryloyloxy groups) and weight average molecular weight of the urethane-based compound having a (meth) acryloyl group. Thereby, since the range of the material which can be selected without increasing a viscosity excessively becomes wide, the viscosity of a resin composition can be adjusted easily. The viscosity of the resin composition can be lowered by using a solvent, but the amount of the solvent can be reduced by using a urethane-based compound having a (meth) acryloyl group with an appropriate number of functional groups and weight average molecular weight. can do. By reducing the amount of the solvent, it is easy to maintain good characteristics and reliability of the cured resin layer.

  The number of functional groups of the urethane-based compound having a (meth) acryloyl group is preferably 2 to 15, more preferably 2 to 12, and still more preferably 2 to 10.

  The weight average molecular weight (Mw) of the urethane compound having a (meth) acryloyl group is preferably 950 to 25000. The weight average molecular weight is more preferably 950 to 15000 from the viewpoint of improving coatability, and further preferably 950 to 11,000 from the viewpoint of compatibility.

As the urethane compound having a (meth) acryloyl group, a compound represented by the following general formula (11) is preferable from the viewpoints of heat resistance after curing, strength of a resin layer having a pattern, and adhesion.

In formula (11), R ²¹ and R ²² each independently represent a divalent organic group. Specific examples thereof include a group having 1 to 20 carbon atoms including a linear or branched alkylene group having 1 to 15 carbon atoms and an alicyclic group which may have a substituent. Here, the alicyclic group is a group having a structure in which carbon atoms are cyclically bonded. q is an integer greater than or equal to 1, for example, 1-5. R ²² is preferably a divalent group represented by the following structure.

  Typical examples of urethane compounds having a (meth) acryloyl group include compounds represented by the following formulas (12), (13), (14), (15) and (16). It is not limited to.

（式（１２）中、ｍは５〜２０の整数を示す。）

(In formula (12), m represents an integer of 5 to 20.)

（式（１３）中、ｍは５〜２０の整数を示す。）

(In formula (13), m represents an integer of 5 to 20.)

（式（１４）中、ｍは５〜２０の整数を示す。）

(In formula (14), m represents an integer of 5 to 20.)

（式（１５）中、ｍは５〜２０の整数を示す。）

(In the formula (15), m represents an integer of 5 to 20.)

（式（１６）中、ｍは５〜２０の整数を示す。）

(In formula (16), m represents an integer of 5 to 20.)

  As a commercial item of the compound represented by each said formula, UN-952 (functional group number: 10, Mw: 6500-11000) which is a compound represented by the said Formula (12), etc. are mentioned.

  In addition, examples of commercially available urethane compounds having an acryloyl group (compounds having an acryloyloxy group) include, for example, UN-904 (number of functional groups: 10, Mw: 4900), UN-333 (number of functional groups: 2, Mw: 5000), UN-1255 (functional groups: 2, Mw: 8000), UN-2600 (functional groups: 2, Mw: 2500), UN-6200 (functional groups: 2, Mw: 6500), UN-3320HA (functional) Group: 6, Mw: 1500), UN-3320HC (functional group number: 6, Mw: 1500), UN-9000 PEP (functional group number: 2, Mw: 5000), UN-9200A (functional group number: 2, Mw: 15000) , UN-3320HS (functional group number: 15, Mw: 4900), UN-6301 (functional group number: 2, Mw: 33000) (above All are Negami Kogyo Co., Ltd., trade name), TMCH-5R (Hitachi Chemical Co., Ltd., trade name; number of functional groups: 2, Mw: 950), KRM8452 (number of functional groups = 10, Mw = 1200), and EBECRYL 8405 (urethane). Acrylate / 1,6-hexanediol diacrylate = 80/20 addition reaction product, number of functional groups: 4, Mw: 2700) (all of these are Daicel Cytec Co., Ltd., trade name).

  Examples of commercially available urethane compounds having a methacryloyl group (compounds having a methacryloyloxy group) include UN-6060 PTM (Negami Kogyo Co., Ltd., trade name; number of functional groups: 2, Mw: 6000), JTX-0309 (Hitachi). Kasei Co., Ltd., trade name) and UA-21 (Shin Nakamura Chemical Co., Ltd., trade name).

  The content of the urethane-based compound having a (meth) acryloyl group is preferably 10% by mass or more, more preferably 30% by mass or more, and more preferably 30% by mass or more, based on the total amount of the component (a ′) from the viewpoint of improving heat resistance. Preferably it is 50 mass% or more. When this content is 10% by mass or more, various properties required for coating properties and a cured product of the resin composition can be maintained at a higher level. Further, the content is preferably 95% by mass or less, more preferably 85% by mass or less, and still more preferably 75% by mass or less with respect to the total amount of the component (a ′).

  In the resin composition, as the component (a ′), a urethane compound having a (meth) acryloyl group and other polyfunctional (meth) acrylic monomers may be used in combination. Examples of the polyfunctional (meth) acrylic monomer include a (meth) acrylate compound having an amide bond, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, and a bisphenol A-based (meta ) A compound obtained by reacting an acrylate compound or a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, and a (meth) acrylic acid alkyl ester copolymer having an ethylenically unsaturated group. These can be used individually by 1 type or in combination of 2 or more types. In addition, the resin composition according to the present embodiment may contain a monofunctional (meth) acrylic monomer separately from the component (a ′). Examples of the monofunctional (meth) acrylic monomer include the component (a) described above.

(B ′) Thermal Polymerization Initiator As the (b ′) thermal polymerization initiator according to this embodiment, the same (c-1) thermal polymerization initiator as that in the resin composition of the first embodiment may be used. it can.

  The blending amount of component (b ′) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, and still more preferably 0.1 to 100 parts by mass of the total amount of component (a ′). 5 to 10 parts by mass.

  In this embodiment, (b ′) a thermal polymerization initiator is blended, but a photopolymerization initiator may be blended depending on the situation. As a photoinitiator, the thing similar to the (c-2) photoinitiator in the resin composition of 1st Embodiment is mentioned.

  The blending amount of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.75 with respect to 100 parts by mass of the total amount of the component (a ′). -5 parts by mass.

(C ′) Hindered phenolic compound The (c ′) hindered phenolic compound according to the present embodiment has a phenolic hydroxyl group in the molecule, and the peroxide radical (ROO. ). The hindered phenol compound is not particularly limited as long as it provides the above action, but 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′- Di-t-butyl-4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t- Butyl-4-hydroxybenzyl) isocyanurate, 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol) and triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) propionate]. These can be used individually by 1 type or in combination of 2 or more types.

  As the hindered phenol compound, a commercially available one may be used, or it may be produced according to a conventional method.

  (C ') As a commercial item of an ingredient, Adeka tab AO series (30, 50, 60, 70, 80, 330, etc.) of ADEKA Corporation, Irganox series (Irganox 1010, 1035, 1076) of Ciba Japan Co., Ltd. 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, etc.).

  The content of the component (c ′) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the component (a ′) from the viewpoint of compatibility and colorability.

(D ′) Thioether compound The (d ′) thioether compound according to this embodiment is a compound having a thioether bond in the molecule, and is preferably a compound represented by the following general formula (17).

［式（１７）中、Ｒ^ａは同一でも異なっていてもよく、炭素数１０〜２０のアルキル基を示す。］

[In Formula (17), ^Ra may be the same or different and represents an alkyl group having 10 to 20 carbon atoms. ]

  As the thioether compound, a commercially available sulfur-based antioxidant may be used, or it may be produced according to a conventional method.

Examples of the thioether compound represented by the formula (17) include dilauryl thiodiisopropionate (S (CH ₂ CH ₂ COOC ₁₂ H ₂₅ ) ₂ ), ditridecylthiodipropionate (S (CH ₂ CH ₂ COOC ₁₃ H ₂₇ ) ₂ ), dimyristyl thiodipropionate (S (CH ₂ CH ₂ COOC ₁₄ H ₂₉ ) ₂ ), lauryl stearyl thiodipropionate ((H ₂₅ C ₁₂ O (O) CCH ₂ CH ₂ ) S (CH ₂ CH ₂ COOC ₁₈ H ₃₇ ))) and distearyl thiodipropionate (S (CH ₂ CH ₂ COOC ₁₈ H ₃₇ ) ₂ ).

  The content of the thioether-based compound is preferably 0.01 to 2 parts by mass with respect to 100 parts by weight of the total amount of the component (a ′) from the viewpoints of suppressing oxidative deterioration of the cured product, compatibility and colorability. .

(E ′) Compound having thiol group The compound having (e ′) thiol group according to this embodiment is preferably a compound having a boiling point of 250 ° C. or higher. Further, a compound having an action of addition reaction to a conjugated system generated in the resin by heat to cleave the conjugated structure is preferable, and in particular, a hydrogen donor that does not exhibit basicity capable of decomposing quinone is more preferable. . Moreover, it is preferable that it is a compound which has three or more thiol groups.

［式（１８）中、Ｅはｐ価の有機基を示し、ｐは１〜６の整数を示す。］ As the compound having a thiol group in the molecule, a compound represented by the following general formula (18) is preferable.

[In formula (18), E shows a p-valent organic group, and p shows the integer of 1-6. ]

  Examples of such compounds include 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and pentane. An example is erythritol tetrakis (3-mercaptobutyrate). These compounds are available from Showa Denko KK as Karenz MT series (Karenz MT NR1, Karenz MT PE1, etc.). These compounds can be used individually by 1 type or in combination of 2 or more types.

  Content of the compound which has a thiol group in a molecule | numerator is 0.01-2 mass parts with respect to 100 mass parts of total amounts of (a ') component from a viewpoint of oxidative degradation suppression of cured | curing material, compatibility, and coloring property. It is preferable that

(Organic solvent)
In addition to the components (a ′), (b ′), (c ′), (d ′), and (e ′), the resin composition according to the present embodiment contains, as necessary, optional components described later as an organic solvent. It can be dissolved or dispersed in a varnish. As an organic solvent, the thing similar to the resin composition of the said 1st Embodiment can be used.

  The resin composition according to this embodiment may contain a coupling agent or a filler. As the coupling agent or filler, the same resin composition as that of the first embodiment can be used.

  The resin composition according to this embodiment may further contain a binder resin as necessary. Examples of the binder resin include acrylic polymers, epoxy resins, urethane resins, and polyimide resins. From the viewpoint of transparency, the binder resin is preferably an acrylic polymer, and more preferably the component (a) described above.

  In the production of the varnish when the filler is added to the resin composition according to the present embodiment, in consideration of dispersibility, a physical shearing force is applied by a reiki machine, a three roll, a ball mill, a bead mill, etc. It is preferable to use after sufficiently dispersing so that there is no next aggregated particle. The above dispersion methods can be used in combination.

  Further, the mixing time can be shortened by mixing the filler and the low molecular weight material in advance and then blending the high molecular weight material.

  There is no particular limitation on the method of stirring and mixing each component uniformly, but rotation and revolution of a dissolver, static mixer, homogenizer, ultrasonic homogenizer, paint shaker, ball mill, planetary mixer, mix rotor, universal agitator, etc. In addition to the type stirrer, a method using a laika machine, a kneading apparatus such as a three-roller, and the like can be mentioned, and these can be used in combination as appropriate. After the varnish is formed, it is preferable to remove bubbles in the varnish. In this sense, the rotation and revolution type stirrer is preferably used because it can simultaneously perform mixing and dissolution and removal of bubbles.

  The resin composition according to the present embodiment further includes a curing retarder, a hindered amine light stabilizer, an ultraviolet absorber, an inorganic filler, an organic filler, a coupling agent, an adhesion imparting agent, and a polymerization prohibition as necessary. An agent, a plasticizer, a release agent, an antistatic agent, a flame retardant and the like may be added as appropriate, alone or in combination.

  The resin composition according to the present embodiment may further include a moisture absorbent such as calcium oxide and magnesium oxide, a fluorosurfactant, a nonionic surfactant, a wetting improver such as a higher fatty acid, silicone oil, and the like as necessary. An anti-foaming agent, an ion trapping agent such as an inorganic ion exchanger, or the like can be added as appropriate, alone or in combination.

<Method for producing flexible transparent substrate>
The first and second resin compositions may be applied directly to the inorganic glass film 1 or may be applied to the inorganic glass after being formed into a film.

  Examples of the method for applying the resin composition include a dispensing method, a spin coating method, a die coating method, a knife coating method, and the like. Method or die coating method is preferred.

The above-mentioned resin composition can be formed into a film by, for example, the following method.
By applying the above resin composition uniformly on a support film and heating the solvent used sufficiently at a temperature such as 60 to 200 ° C. for 0.1 to 30 minutes, a film-like resin is obtained. Form a composition. At this time, the solvent amount of the resin composition, the viscosity, and the initial coating thickness (when using a coater such as a die coater or a comma coater, the coater and supporting film are used so that the film-like resin composition has a desired thickness. Adjusting the gap), adjusting the drying temperature, air volume, etc.

  The support film preferably has flatness. For example, since a support film such as a PET film has high adhesion due to static electricity, a smoothing agent may be used to improve workability. Depending on the type and temperature of the smoothing agent, fine unevenness may be transferred to the adhesive to lower the flatness. Therefore, it is preferable to use a support film that does not use a smoothing agent or a support film that contains few smoothing agents. A support film such as a polyethylene film is preferable in terms of excellent flexibility, but it is preferable to appropriately select the thickness and density of the support film so that roll marks and the like are not transferred to the resin layer surface during lamination.

  The flexible transparent substrates 10 and 20 are, for example, a method in which a resin layer is formed on the inorganic glass film 1 by coating the resin composition described above, and then the resin layer is cured, or a resin film is pasted on the inorganic glass film. It is manufactured through a method of curing the resin layer after forming the resin layer. Preferably, the resin layer is cured after the resin film is pasted and the resin layer is formed on the inorganic glass film 1. Such a method can be manufactured in a form suitable for the R2R process, and a transparent substrate can be obtained at low cost. In addition, when using the photosensitive resin composition as a resin composition for transparent resin layer formation, after coating the said composition on the whole surface of the inorganic glass film 1, the area | region for the decoration layer 5 by exposure and image development The pattern may be formed.

  The method of forming a resin layer on the inorganic glass film 1 by the pasting step to obtain a transparent substrate is preferably a step of heating and pressure-bonding the resin film to one side or both sides of the inorganic glass film 1, and a resin film after pasting A curing step of curing the resin layer by heating or ultraviolet irradiation treatment. Examples of the method for attaching the resin film include a thermal laminator and a vacuum laminator.

  Any appropriate curing method (for example, under a nitrogen flow) may be employed as the curing step. For example, in the case of heat curing, the drying temperature is typically 120 ° C. to 220 ° C., and the curing time is typically 20 minutes to 180 minutes. After laminating the transparent resin layer 7a and, if necessary, the transparent resin layer 7b at a predetermined position of the inorganic glass film 1, the decoration layer 5 is formed on the remaining portion 1c.

  Next, an example of a process for producing a flexible transparent substrate and an organic EL element will be specifically described.

(1) Preparation of varnish The above-mentioned resin composition components are mixed and kneaded in an organic solvent to prepare a varnish. There is no restriction | limiting in particular in the usage-amount of the organic solvent at the time of using for preparation of a varnish, Although an organic solvent is removed from a resin film by heat drying etc., the amount of organic solvents (residual volatile matter) after resin film preparation Is preferably 0.01 to 3% by weight based on the total weight, more preferably 0.01 to 2% by weight based on the total weight from the viewpoint of heat resistance reliability, and 0.01 to 1.5% by weight based on the total weight. Is more preferable. The above mixing and kneading can be carried out by appropriately combining dispersers such as a normal stirrer, a raking machine, a triple roll, and a ball mill.

(2) Film coating The varnish obtained in the above (1) is coated on a substrate to form a varnish layer. As the substrate, a polyethylene terephthalate film, a polyimide film, a polyester film, a polypropylene film, a polyetherimide film, a polyether naphthalate film, a methylpentene film, or the like can be used. For coating, a polyethylene terephthalate film, a polyimide film, or the like can be used, and the coating thickness is determined in consideration of the final thickness of the resin film, but is preferably 5 to 250 μm.

(3) Heat-drying The base material which apply | coated the varnish obtained by said (2) is heat-dried. The conditions for the heat drying are not particularly limited as long as the solvent used is sufficiently volatilized, but it is usually carried out by heating at 60 to 200 ° C. for 0.1 to 90 minutes. After heat drying, the substrate can be removed to obtain a resin film (B stage film).

  From the viewpoint of preventing cracking of the flexible transparent substrate, the thickness of the resin film for the first transparent resin layer 7a is preferably 1 to 30 μm, more preferably 5 to 20 μm. From the same viewpoint, the thickness of the resin film for the second transparent resin layer 7b is preferably 1 to 500 μm, more preferably 5 to 70 μm. More preferably, it is preferable to set it as 10-50 micrometers.

(4) Vacuum lamination The resin film obtained in the above (3) is attached to a predetermined position on the first surface 1 a of the inorganic glass film 1. The method for attaching is not limited as long as the resin film can be applied sufficiently uniformly without bubbles. When pasting by vacuum lamination, it is usually pasted at 40 to 120 ° C. and 0.2 to 1.5 MPa. If the temperature is lower than 40 ° C. or the pressure is lower than 0.2 MPa, the resin may not adhere to the inorganic glass film 1, and if the temperature is higher than 120 ° C., the resin film may be denatured. There is. Moreover, when a pressure is larger than 1.5 MPa, the inorganic glass film 1 may crack. When the second transparent resin layer 7b is further provided on the second surface 1d of the inorganic glass film 1, the resin film is attached to the second surface 1d of the inorganic glass film 1 by the same method.

(5) Heat curing The resin-bonded glass film obtained in the above (4) is heated in an oven to cure the resin component to obtain a transparent substrate.

(6) Printing of decoration layer The part which the 1st surface 1a of the inorganic glass film 1 of the laminated body obtained by said (5) is exposed (part in which the 1st transparent resin layer 7a is not laminated | stacked). In addition, the flexible transparent substrates 10 and 20 are obtained by laminating the decorative layer 5. The decorative layer 5 can be laminated using, for example, screen printing, gravure printing, other appropriate printing, or sublimation (thermal) transfer or foil transfer (so-called hot stamp). The decorative layer 5 can also be laminated before forming the first transparent resin layer 7 a on the first surface 3 of the inorganic glass film 1. From the viewpoint of preventing bleeding or the like of the decorative layer 5, it is preferable to form the decorative layer 5 after the first transparent resin layer 7a is laminated.

(7) Production of electrode IZO is sputtered on a 750 μm glass plate by vacuum deposition.

(8) Production of EL element An organic EL element is formed on the substrate obtained in (7), and the upper layer is sealed.

  Since the flexible transparent substrates 10 and 20 which concern on this embodiment are using the inorganic glass film 1, they have gas-barrier property and moisture-proof property. Moreover, since the inorganic glass film 1 is covered with the transparent resin layer 7a or this and the transparent resin layer 7b, the inorganic glass film 1 is not easily cracked and is easy to handle, and is thin and lightweight.

  The flexible transparent substrates 10 and 20 can be suitably used for, for example, a liquid crystal display device, a plasma display device, a display device such as an organic EL, an illumination device such as an incandescent bulb, a fluorescent lamp, a lamp, an LED, and an organic EL device. .

  Hereinafter, the evaluation test and the result of the organic EL element produced using the above-mentioned first or second resin composition will be described.

(Synthesis of acrylic polymer 1)
Acrylic acid tricyclo [5.2.1.0 ^2,6 ] dec-8-yl (FA-513A, Hitachi Chemical Co., Ltd., trade name) 300 g, butyl acrylate (BA) 350 g, butyl methacrylate (BMA) 300 g , 50 g of glycidyl methacrylate (GMA) and 50 g of 2-ethylhexyl methacrylate (2EHMA) were mixed, and 5 g of dilauroyl peroxide and 0.45 g of n-octyl mercaptan as a chain transfer agent were dissolved in the resulting monomer mixture. To give a mixed solution.
As a suspending agent, 0.44 g of polyvinyl alcohol and 2000 g of ion-exchanged water were added to a 5 L autoclave equipped with a stirrer and a condenser. Further the mixture was added with stirring, stirring rotational speed 250min ^-1, 5 hours at 60 ° C. under nitrogen atmosphere and then polymerized for 2 hours at 90 ° C., to obtain a resin particle (polymerization ratio, in mass method 99 %Met.). The resin particles were washed with water, dehydrated and dried to obtain an acrylic polymer 1. The weight average molecular weight of the obtained acrylic polymer 1 was Mw = 480,000.

(Preparation of resin film 1)
Each component was mix | blended with the compounding ratio shown in Table 1, and the solution of the resin composition was obtained. The obtained resin composition solution was uniformly coated on a glass plate using a spin coater and dried on a hot plate at 100 ° C. for 5 minutes to form a resin film 1 having a dried film thickness of 10 μm. .

(Preparation of resin film 2)
Each component was mix | blended with the compounding ratio shown in Table 2, and the solution of the resin composition was obtained. The obtained resin composition solution was uniformly applied on a glass plate using a spin coater and dried on a hot plate at 100 ° C. for 5 minutes to form a resin film 2 having a dried film thickness of 10 μm. .

In addition, the component in Table 1 and 2 shows the following component specifically.
A-DOG: Shin-Nakamura Chemical Co., Ltd. (trade name), chemical substance name: Dioxane glycol diacrylate park mill D: NOF Corporation (trade name) chemical substance name; dicumyl peroxide, 1 hour half-life temperature 135.7 ° C, 10 hour half-life temperature 116.4 ° C
KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd. (trade name), silane coupling agent, chemical substance name; 3- (trimethoxysilyl) propyl PGMEA methacrylate: manufactured by Kanto Chemical Co., Ltd .; chemical substance name: propylene glycol 1- Monomethyl ether 2-acetate AO-80: manufactured by ADEKA Corporation (trade name), hindered phenol antioxidant, chemical name; bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) Propionic acid] (2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl)
NR1: manufactured by Kyoeisha Chemical Co., Ltd. (trade name), chemical name; 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H , 5H) -trione AO-503: manufactured by ADEKA Corporation (trade name), thioether-based antioxidant, chemical substance name; ditridecyl 3,3-thiobispropionate UN-952: manufactured by Negami Kogyo Co., Ltd. (trade name) , Name of chemical substance; urethane acrylate oligomer, number of functional groups: 10, Mw = 6500 to 11000
BPE-100: Shin-Nakamura Chemical Co., Ltd. (trade name), chemical substance name; ethylene oxide modified bisphenol A dimethacrylate AO-412S: ADEKA Co., Ltd. (trade name), thioether antioxidant, chemical substance name; bis [3- (dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediylcarenes MT NR1: manufactured by Showa Denko KK (trade name) ), Chemical name; 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione DMAc: Kanto Chemical Co., Inc. Company, chemical name; dimethylacetamide

Example 1
One side surface of an inorganic glass film (OA, manufactured by Nippon Electric Glass Co., Ltd.) having a thickness of 50 μm and a length of 100 mm × width of 100 mm was washed with N ₂ blow, and the length of 130 mm length × width 130 mm under the condition of 0.5 MPa / 65 ° C./60 s The resin film 1 was vacuum laminated. A heat curing treatment was performed at 180 ° C. for 120 minutes to obtain a transparent substrate having a thickness of 60 μm.

(Example 2)
A transparent substrate was obtained in the same manner as in Example 1 except that the resin film 2 was used in place of the resin film 1.

(Comparative Example 1)
A glass plate having a thickness of 700 μm was used as a substrate.

(Comparative Example 2)
A glass film (without a transparent resin layer) having a thickness of 50 μm was used as a substrate.

(Comparative Example 3)
A PEN film having a thickness of 50 μm was used as a substrate.

(Comparative Example 4)
Resin film 1 was used as a substrate.

(Comparative Example 5)
Resin film 2 was used as a substrate.

  About the board | substrate (flexible transparent substrate) of an Example and a comparative example, the 3 mm bending test shown below, a total light transmittance test, a 5% weight reduction temperature test, and the light emission holding time test were done, respectively. The results are shown in Table 3.

(3mm bending test)
A 5 cm × 5 cm substrate was wound around a 3 cm diameter cylinder (manufactured by SUS), and it was OK if it could be wound without cracking.

(Total light transmittance test)
Measurement was performed with a total light transmittance measuring device. Air was used as a reference.

(5% weight loss temperature test)
The degree of weight loss was measured by Tg / DTA. (Raising rate: 5 ° C / min)

(Light emission retention time test)
The manufactured organic EL device was placed in a constant temperature and humidity tester set to 85 ° C. and 85% RH. If the light emission could be confirmed after each time of 1, 2, 4, 8, 16, 25, 50, 100, 150, 200, 250 hours, it was determined as OK.

(Substrate weight measurement)
The weight of the 1 cm ² substrate was measured by a weigh scale.

  From Table 3, Examples 1 and 2 indicate that the transparency and light emission retention time are the same level as in Comparative Example 1, and that the weight is reduced. Further, since the 5% weight loss temperature is also 200 ° C. or higher, it can be seen that the transparent substrate according to the example has low outgas and high reliability. On the other hand, since the comparative example 2 generate | occur | produces the crack at the time of a bending test, it has shown that the transparent resin layer has reduced the crack among the board | substrate structures which concern on embodiment. Furthermore, the organic EL element using the transparent substrate according to the example has a longer light emission retention time and higher reliability than Comparative Examples 3, 4, and 5. This indicates that, among the substrate configurations according to the examples, reliability is maintained by the high water vapor barrier property of the inorganic glass film.

  DESCRIPTION OF SYMBOLS 1 ... Inorganic glass film, 1a ... 1st surface, 1b ... Peripheral part, 1c ... Remaining part, 1d ... 2nd surface, 5 ... Decorating layer, 7a ... 1st transparent resin layer, 7b ... 2nd Transparent resin layer, 10, 20 ... flexible transparent substrate.

Claims (16)

An inorganic glass film having a thickness of 10 to 100 μm;
A decorative layer laminated on at least a part of the peripheral edge of the first surface of the inorganic glass film;
A first transparent resin layer laminated on the remaining portion of the first surface of the inorganic glass film;
With
The first transparent resin layer is
(A1) an acrylic polymer having a weight average molecular weight of 100,000 or more;
(B1) a compound having at least two (meth) acryloyl groups;
(C1) a polymerization initiator;
A cured product of the first composition containing
The structural unit which has a nitrogen atom containing group in said (a1) component is 5 mass% or less of the whole acrylic polymer, and (a1) component contains the structural unit which has a functional group.   The flexible transparent substrate according to claim 1, wherein the component (a1) includes a structural unit having an alicyclic structure.   The flexible transparent substrate according to claim 1, wherein the functional group of the component (a1) includes an epoxy group.   The flexible transparent substrate according to any one of claims 1 to 3, wherein the first composition further contains (d1) an antioxidant. A second transparent resin layer laminated on the second surface opposite to the first surface of the inorganic glass film;
The second transparent resin layer is
(A2) an acrylic polymer having a weight average molecular weight of 100,000 or more;
(B2) a compound having at least two (meth) acryloyl groups;
(C2) a polymerization initiator;
A cured product of the second composition containing
The structural unit having a nitrogen atom-containing group in the component (a2) is 5% by mass or less of the whole acrylic polymer, and the component (a2) includes a structural unit having a functional group. A flexible transparent substrate according to Item.   The flexible transparent substrate according to claim 5, wherein the component (a2) includes a structural unit having an alicyclic structure.   The flexible transparent substrate according to claim 5 or 6, wherein the functional group of the component (a2) includes an epoxy group.   The flexible transparent substrate according to any one of claims 5 to 7, wherein the second composition further contains (d2) an antioxidant.   The flexible transparent substrate according to any one of claims 5 to 8, wherein the visible light transmittance of the second transparent resin layer is 80% or more. An inorganic glass film having a thickness of 10 to 100 μm;
A decorative layer laminated on at least a part of the peripheral edge of the first surface of the inorganic glass film;
A first transparent resin layer laminated on the remaining portion of the first surface of the inorganic glass film;
With
The first transparent resin layer is
(A ′) a compound having at least two ethylenically unsaturated groups;
(B ′) a thermal polymerization initiator;
(C ′) a hindered phenol compound,
(D ′) a thioether compound,
(E ′) a compound having a thiol group;
A flexible transparent substrate comprising a cured product of a third composition containing   The flexible transparent substrate according to claim 10, wherein the component (a ′) includes a urethane compound having a (meth) acryloyl group.   The flexible transparent substrate according to any one of claims 1 to 11, wherein the visible light transmittance of the first transparent resin layer is 80% or more.   The flexible transparent substrate according to any one of claims 1 to 12, wherein a thickness of the first transparent resin layer is 1 to 30 µm.   The surface of the said decoration layer and the surface of the said 1st transparent resin layer, Comprising: The surface on the opposite side to the said inorganic glass film is mutually formed in the same surface, The any one of Claims 1-13 The flexible transparent substrate as described.   The flexible transparent substrate according to any one of claims 1 to 14, wherein the decorative layer has a thickness of 1 to 30 µm.   The flexible transparent substrate according to any one of claims 1 to 15, which is used for a display device or a lighting device.

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