JP2016107441A - Transparent substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent substrate that is excellent in process adaptability, gas barrier property, transparency and heat resistance, as well as that is lighter weight as compared with the conventional glass substrate and that is excellent in bending resistance, and furthermore that is adaptable to the flexible device roll-to-roll process.SOLUTION: Provided is a transparent substrate including an inorganic glass, and a resin layer formed on at least one principal surface of the inorganic glass, and in which the total light transmittance of the resin layer after heating the resin under a condition of 180°C for 120 minutes is 80% or more, the haze of the resin layer after heating under said condition is 2.0% or less, and the yellowness index (YI value) of the resin layer after heating the resin layer under a condition of 200°C for 120 minutes is 6.0 or less, and in which the mass per unit area of the transparent substrate is 0.2 g/cmor less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transparent substrate.

  In recent years, functional substrates used in the fields of lighting, displays, solar cells, and the like have been increasingly demanded for weight reduction for the purpose of safety and cost reduction.

  However, the thickness of a glass plate generally used as a substrate is large, and the weight of the entire substrate is heavy. Although there is an example in which a thin glass plate is used in order to reduce the weight, the handling property is extremely low because the thin glass is easily broken.

  An organic EL element is mentioned as one of the typical functional substrates. Usually, an organic EL element is comprised by laminating | stacking a transparent conductive inorganic film | membrane, a hole injection layer, a hole transport layer, a light emitting layer, and a cathode on a board | substrate, and sealing with glass. Representative transparent conductive inorganic films include ITO, IZO, IGZO, TFT, and the like.

  Properties required for the organic EL element substrate include process suitability (handleability), gas and water vapor barrier properties (hereinafter referred to as gas barrier properties), transparency, heat resistance, and the like. Although a thick glass substrate satisfies these characteristics, there are problems such as an increase in the weight of the entire substrate and a low bending resistance as described above.

  On the other hand, it is also conceivable to use a resin film as the substrate instead of the glass substrate. When a resin film is used as a substrate, it is excellent in lightening effect and bending resistance.

  Therefore, a substrate in which a resin film is laminated on a glass plate has been proposed (see, for example, Patent Documents 1 to 3).

JP 2003-39597 A JP 2006-205725 A JP 2008-37094 A

  However, since the conventional resin film has a very low gas barrier property, the moisture resistance reliability of the organic EL element such as the light emission retention is lost. Although there are attempts to maintain gas barrier properties by filling the resin layer with fillers, water molecules, components that adsorb oxygen, and the like, a resin layer containing these components is inferior in transparency.

  Furthermore, when exposed to high temperatures in the manufacturing process of the organic EL element, particularly in the vacuum deposition process, the drying process, etc., the conventional resin film generates outgas, and the light emitting characteristics and reliability of the organic EL element are reduced. There is also a problem.

  Therefore, the present invention is excellent in process compatibility, gas barrier properties, transparency and heat resistance, is lighter than conventional glass substrates, has excellent bending resistance, and roll-to-roll of flexible devices. It is an object to provide a transparent substrate that can be adapted to the process.

The present invention provides the following [1] to [7].
[1] A transparent substrate comprising inorganic glass and a resin layer formed on at least one main surface of the inorganic glass, wherein the resin layer is heated at 180 ° C. for 120 minutes. The resin after heating at 200 ° C. for 120 minutes, the resin layer having a total light transmittance of 80% or more and a haze of 2.0% or less after heating under the above conditions The transparent substrate whose yellowness (YI value) of a layer is 6.0 or less and whose mass per unit area of the said transparent substrate is 0.2 g / cm < ² > or less.
[2] The transparent substrate according to [1], wherein a 5% mass reduction temperature of the resin layer is 150 ° C. or higher.
[3] The transparent substrate according to [1] or [2], wherein a peel strength between the resin layer and the inorganic glass is 50 N / m or more.
[4] The transparent substrate according to any one of [1] to [3], in which a flexural modulus (25 ° C.) of a two-layer configuration including an inorganic glass and a resin layer is 0.01 to 80 GPa.
[5] The resin layer 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. The structural unit formed from the resin composition and having a nitrogen atom-containing group in the acrylic polymer of the component (a) is 5% by mass or less of the entire acrylic polymer, and the component (a) has a functional group. The transparent substrate according to any one of [1] to [4], which is a cured product of a resin composition including a structural unit.
[6] The 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. And (e ′) the transparent substrate according to [1] to [4], which is a cured product of a resin composition containing a compound having a thiol group.
[7] The transparent substrate according to [6], wherein the component (a ′) includes a urethane compound having a (meth) acryloyl group.

  According to the present invention, process compatibility, gas barrier properties, transparency and heat resistance are excellent, lighter than conventional glass substrates, superior in bending resistance, and adaptable to roll-to-roll process of flexible devices. A transparent substrate can be provided.

It is a schematic cross section showing one mode of a transparent substrate of this embodiment. It is a schematic cross section showing one mode of a transparent substrate of this embodiment. It is a schematic cross section which shows the other aspect of the transparent substrate of this embodiment. It is a schematic cross section which shows the other aspect of the transparent substrate of this embodiment. It is a schematic cross section which shows the other aspect of the transparent substrate of this embodiment.

  Hereinafter, although one embodiment of the present invention is described, the present invention is not limited to these embodiments. 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.

  1 and 2 are schematic cross-sectional views showing one aspect of the transparent substrate of the present embodiment. A transparent substrate 10 shown in FIG. 1 has a configuration in which a resin layer (resin cured product layer) 3 is formed on one main surface of an inorganic glass 1. The transparent substrate 20 shown in FIG. 2 has a configuration in which a resin layer (cured resin layer) 3a is formed on one main surface of the inorganic glass 1 and a resin layer (resin cured material layer) 3b is formed on the other main surface. Have

3 and 4 are schematic cross-sectional views showing other aspects of the transparent substrate of the present embodiment. In the transparent substrates 30 and 40 shown in FIGS. 3 and 4, the entire side surface of the inorganic glass 1 is covered with the resin layer (resin cured product layer) 3. The resin layer (resin cured product layer) 3 may protrude from the end of the inorganic glass 1 as shown in the transparent substrate 40. The thickness of the resin layer (resin cured product layer) 3 covering the side surface of the inorganic glass 1 (the thickness of the portion represented by A to D in FIGS. 3 and 4) is preferably 0.1 to 700 μm. . If it is thinner than 0.1 μm, the effect of suppressing cracking of inorganic glass is likely to be low, and if it is 700 μm or more, the weight of the substrate is heavy, and it is compatible with devices that require strong weight reduction such as wearable and flexible. It is likely to be low.
3 and 4, the thicknesses of A and B or C and D may be the same or different, but are preferably the same.

  FIG. 5 is a schematic cross-sectional view showing another aspect of the transparent substrate of the present embodiment. In the transparent substrate 50 shown in FIG. 5, the resin layer (resin cured product layer) 3 protrudes from the side end of the inorganic glass 1. The length of the resin layer (resin cured product layer) protruding from the side end is preferably 0.01 mm or more. In the transparent substrate 50, the resin layer (resin cured product layer) 3 protrudes from both end portions of the inorganic glass 1, but the resin layer (resin cured product layer) 3 protrudes from at least one side end portion. That's fine. Moreover, when the resin cured material layer 3 protrudes from the both ends of the inorganic glass 1, the length of the resin layer (resin cured material layer) protruding from the side edge (represented by E and F in FIG. 5). The lengths of the portions to be formed may be the same or different, but are preferably the same.

  The resin layer is bonded to the glass layer mainly by interaction. As a result, the resin layer and the glass layer are firmly bonded, and a transparent substrate having excellent adhesion can be obtained.

  The total thickness of the transparent substrate is preferably 1000 μm or less, more preferably 500 μm or less, and even more preferably 5 to 300 μm. According to this invention, by having a resin layer as mentioned above, the thickness of inorganic glass can be made much thinner than the conventional glass substrate. That is, even if the resin layer is thin, it can contribute to improvement of impact resistance and toughness. Therefore, the transparent substrate of the present invention having the resin layer is lightweight and thin and has excellent process adaptability.

  The bending elastic modulus (25 ° C.) of the transparent substrate is preferably 0.01 to 80 GPa, more preferably 0.1 to 60 GPa. On the other hand, if it is less than 0.01 GPa, the handling property is impaired such that the substrate cannot withstand its own weight. Moreover, since flexibility will be impaired when it exceeds 80 GPa, it is not preferable.

  The total light transmittance (total light transmittance) in visible light of the resin layer after heating the resin layer of the transparent substrate at 180 ° C. for 120 minutes is 80% or more. More preferably, it is 85% or more. Preferably, the transparent substrate has a reduction rate of the total light transmittance of 5% or less after the heat treatment at 180 ° C. for 120 minutes. If the reduction rate of the total light transmittance is within 5%, a practically acceptable light transmittance can be ensured even if a heat treatment necessary for the manufacturing process of the display element and the solar cell is performed.

  The surface roughness (arithmetic mean roughness) Ra (substantially the surface roughness Ra of the resin layer or the other layer) of the transparent substrate is preferably 50 nm or less, more preferably 30 nm or less, Preferably it is 10 nm or less. The waviness of the transparent substrate is preferably 0.5 μm or less, more preferably 0.1 μm or less. With a transparent substrate having such characteristics, even if the organic EL layer is formed on the resin layer side, the same performance as when formed on glass can be obtained.

  The yellowness (YI value) of the resin layer after heating the resin layer of the transparent substrate at 200 ° C. for 120 minutes is 6 or less, preferably 4 or less, more preferably 3 or less. With a transparent substrate having such characteristics, even if the organic EL layer is formed on the resin layer side, the same performance as when formed on glass can be obtained. Yellowness (YI value) can be measured using a commercially available apparatus.

  The haze of the resin layer after heating the resin layer of the transparent substrate at 180 ° C. for 120 minutes is 2.0%, preferably 1.5% or less, more preferably 1.0% or less. It is. With a transparent substrate having such characteristics, even when an organic EL layer is formed on the resin layer side, the same degree of visibility as when formed on glass can be obtained.

  The peel strength between the resin layer of the transparent substrate and the inorganic glass is 50 N / m or more, more preferably 60 N / m or more. A transparent substrate having such characteristics can maintain good adhesion between the laminated resin layer and the glass.

  The 5% mass reduction temperature of the resin layer of the transparent substrate is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. With a transparent substrate having such characteristics, even when an organic EL layer is formed on the resin layer side, an element lifetime equivalent to that when formed on glass can be obtained.

The mass per unit area of the transparent substrate is 0.2 g / cm ² or less.

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

<Inorganic glass>
Any appropriate inorganic glass can be adopted as long as it is plate-shaped. Examples of the inorganic glass include soda-lime glass, borosilicate glass, aluminosilicate glass, and quartz glass according to the classification according to the composition. Moreover, according to the classification | category by an alkali component, an alkali free glass, a low alkali glass, etc. are mentioned. The content of alkali metal components (for example, Na ₂ O, K ₂ O, Li ₂ O) in the inorganic glass is preferably 15% by mass or less, more preferably 10% by weight or less.

  The thickness of the inorganic glass is preferably 300 μm or less, more preferably 100 to 300 μm, and still more preferably 5 to 70 μm. In the present embodiment, by having a resin layer on at least one side of the inorganic glass, a transparent substrate having excellent process compatibility can be obtained even if the thickness of the inorganic glass is reduced. The lower limit is not particularly limited, but is preferably 5 μm or more from the viewpoint of handleability.

  The total light transmittance of the inorganic glass 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 at a wavelength of 550 nm is preferably 1.4 to 1.65.

The density of the inorganic glass is preferably 2.3 to 3.0 g / cm ³ , more preferably 2.3 to 2.7 g / cm ³ . If it is thin inorganic glass of the said range, the transparent substrate reduced in weight will be obtained.

  Any appropriate method may be adopted as the method for forming the inorganic glass. Typically, the inorganic glass is obtained by melting a mixture containing main raw materials such as silica and alumina, an antifoaming agent such as sodium nitrate and antimony oxide, and a reducing agent such as carbon at a temperature of 1400 to 1600 ° C. After being formed into a thin plate shape, it is produced by cooling. Examples of the method for forming the inorganic glass sheet include an overflow method, a slot down draw method, a fusion method, and a float method. The inorganic glass formed into a plate 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, a commercially available one may be used as it is, or a commercially available inorganic glass may be polished to have a desired thickness. Commercially available inorganic glasses include “7059”, “1737” or “EAGLE 2000” manufactured by Corning, “AN100” manufactured by Asahi Glass Co., Ltd., “NA-35” manufactured by NH Techno Glass Co., Ltd., “OA” manufactured by Nippon Electric Glass Co., Ltd. -10 "," D263 "or" AF45 "manufactured by Schott Corporation.

<Resin layer (resin cured product layer)>
The thickness of the resin layer (cured resin layer) is preferably 0.1 to 700 μm, more preferably 1 to 70 μm, and still more preferably 5 to 50 μm. When the said resin layer (resin cured material layer) is arrange | positioned at the main surface of the both sides of the said inorganic glass, the thickness of each resin layer (resin cured material layer) may be the same, and may differ. Preferably, each resin layer (resin cured product layer) has the same thickness. Furthermore, each resin layer (resin cured product layer) may be composed of the same resin or a resin having the same characteristics, or may be composed of different resins. Preferably, each resin layer (resin cured product layer) is composed of the same resin. Therefore, more preferably, each resin layer (resin cured product layer) is configured to have 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, a curvature and a wave | undulation will become very difficult to produce.

  The relative ratio of the thickness of the resin layer (cured resin layer) is preferably 0.01 to 6, more preferably 0.05 to 3, and still more preferably 0 with respect to the thickness of the inorganic glass. .1 to 1.5. If the ratio of the total thickness of the said resin layer (resin cured material layer) is such a range, the transparent substrate which is excellent in a flexibility and dimensional stability can be obtained.

  The total light transmittance of the resin layer after heating the resin layer (resin cured product layer) at 180 ° C. for 120 minutes is 80% or more. It is preferable that the 5% mass reduction | decrease temperature of the resin layer (resin cured material layer) in the said resin layer (resin cured material layer) is 150 degreeC or more. The total light transmittance and the 5% mass reduction temperature can be measured by, for example, the methods described in Examples.

  Such a resin layer (resin cured product layer) can be obtained, for example, by curing the resin composition of the following first embodiment or second embodiment.

<Resin Composition of First Embodiment>
The resin composition of the first embodiment comprises (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. contains. In addition, the structural unit which has a nitrogen atom containing group in the acrylic polymer of (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 the present embodiment refers to a polymer obtained by polymerizing one acrylic monomer having one (meth) acryloyl group in the molecule, or a copolymer obtained by combining two or more. 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 more preferable to use an epoxy group-containing monomer such as glycidyl (meth) acrylate. Furthermore, 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 based on the total amount of the acrylic polymer. More preferably, it 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 5% by mass or less and 3% by mass or less of the entire acrylic polymer. Preferably, it is more preferably 1% by mass or less, and it is particularly preferable that no structural unit having a nitrogen atom-containing group is contained. 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. The structural unit having a nitrogen atom-containing group is preferably 5% by mass or less based on the entire acrylic polymer, since coloring due to nitrogen oxides can be suppressed to a higher degree.

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 Aromatic vinyl compounds such as tylene, α-fluorostyrene, α-chlorostyrene, α-bromostyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene, methoxystyrene, styrene, cyclopentyl (meth) acrylate, (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.

  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.

［一般式（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。］

[In General 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. 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. ]

The R ^2, for example, those represented by the following formula (2).

［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。］

[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 use amount of the acrylic polymer having a weight average molecular weight including the structural unit having a functional group of 100,000 or more is 10 parts by mass with respect to 100 parts by mass of the compound having at least two (meth) acryloyl groups of the following component (b). -400 mass parts is preferable. When it is in 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 still more 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 as the component (b) according to this embodiment is not particularly limited, and has a polyfunctional (meth) acrylic monomer having an alicyclic skeleton and an aliphatic skeleton. Examples thereof include a polyfunctional (meth) acrylic monomer, a polyfunctional (meth) acrylic monomer having a dioxane glycol skeleton, and a polyfunctional (meth) acrylic monomer having a functional group. 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) Coal diacrylate, 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, hydroxypivalate 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 preferred Ethylene oxide from 5 to 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, (c1) a thermal polymerization initiator, (c2) a photopolymerization initiator, or both can be used.

  (C1) As a thermal polymerization initiator, t-hexyl peroxypivalate (perhexyl PV, NOF Corporation trade name; 1 hour half-life temperature 71.3 ° C., 10 hour half-life temperature 53.2 ° C.), di- Lauroyl peroxide (Perhexyl L, trade name of NOF Corporation; 1 hour half-life temperature 79.3 ° C., 10 hour half-life temperature 61.6 ° C.), di (3,5,5-trimethylhexanoyl) peroxide ( Parroyl 355, NOF Corporation trade name; 1 hour half-life temperature 76.8 ° C., 10 hour half-life temperature 59.4 ° C.), 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexano Art (Perocta O, NOF Corporation 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 NOF Corporation trade name: 1 hour half-life temperature 92.1 ° C, 10 hour half-life temperature 72.1 ° C), benzoyl peroxide + water (Nyper BW, NOF Corporation trade name; 1 hour half-life temperature 92 0.degree. C., 10 hour half-life temperature 73.6.degree. C., 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane (Perhexa TMH, NOF CORPORATION trade name; half an hour) Period temperature 106.4 ° C., 10 hour half-life temperature 86.7 ° C., 1,1-di (t-hexylperoxy) cyclohexane (Perhexa HC, trade name of NOF Corporation; 1 hour half-life temperature 107.3) ℃, 10 hours half-life temperature 87.1 ℃, t-hexyl peroxyisopropyl monocarbonate (Perhexyl I, NOF Corporation trade name; 1-hour half-life temperature 114.6 ℃, 10-hour half-life temperature) 95.0 ° C), t-butyl peroxyisopropyl monocarbonate (Perbutyl I, NOF Corporation trade name; 1 hour half-life temperature 118.4 ° C, 10-hour half-life temperature 98.7 ° C), dicumyl par Oxide (Park Mill D, NOF Corporation trade name; 1 hour half-life temperature 135.7 ° C., 10 hour half-life temperature 116.4 ° C.), n-butyl 4,4-bis (t-butylperoxy) valerate ( Perhexa V, NOF Corporation trade name; 1 hour half-life temperature 126.5 ° C., 10 hour half-life temperature 104.5 ° C.) and other organic peroxides, 2,2′-azobisisobutyronitrile, 1 , 1 '-(cyclohexane-1,1-carbonitrile) -2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), etc. Etc. The.

  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 blending amount of the component (c1) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, and still more preferably with respect to 100 parts by mass of the total amount of the components (a) and (b). Is 0.5 to 10 parts by mass.

  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.

  (C2) Photoinitiators include acyl phosphine oxides, oxime esters, aromatic ketones, quinones, benzoin ether compounds, benzyl derivatives, 2,4,5-triarylimidazole dimers, acridine derivatives, coumarins Compounds, N-phenylglycine derivatives, and the like. In addition, the photoinitiator (c2) 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 (c2) 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′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethyl. Aminobenzophenone, 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-propan-1-one (IRGACURE-907, BASF, trade) Name), 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) Benzyl] phenyl} -2-methyl - propan-1-one (IRGACURE-127, BASF Corp., trade name) and the like.

  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, etc. are 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.

  (C2) 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 with respect to 100 parts by mass of the total amount of the components (a) and (b). More preferably, it is 0.75-5 mass parts.

<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 can 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.

  Examples of the zircoaluminate coupling agent include compounds represented by the following general formula (3).

（一般式（３）中、Ｒはカルボキシル基又はアミノ基を示す。）

(In general 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 Rhone-Poulenc.

  0.1-20 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (c) components, and, as for the compounding quantity of a coupling agent, 1-15 mass parts is more preferable. 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 antifoaming 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, and 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.

<Resin Composition of Second Embodiment>
The resin composition of the second embodiment includes (a ′) a compound having at least two ethylenically unsaturated groups, (b ′) a thermal polymerization initiator, (c ′) a hindered phenol compound, and (d ′) a thioether. 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 of the component (a ′) 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) Coal diacrylate, 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, hydroxypivalate 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 preferred Ethylene oxide from 5 to 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 general 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 of the above formulas, UN-952 (Negami Kogyo Co., Ltd., trade name, number of functional groups: 10, Mw: 6500 to 11000) which is a compound represented by the above formula (12), etc. Is 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 the present embodiment, the same (c1) thermal polymerization initiator as that in the resin composition of the first embodiment can be used.

  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 (c2) 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 Phenol Compound>
The hindered phenol compound of the component (c ′) according to the present embodiment has a phenolic hydroxyl group in the molecule, and has the ability to capture peroxide radicals (ROO.) Generated in the resin due to heat. A compound. 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 ′) component 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).

［一般式（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 General Formula (17), R ^a 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 general 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) can be mentioned.

  The content of the thioether-based compound is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass 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 a thiol group>
The compound having a thiol group as the component (e ′) 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.

  As the compound having a thiol group in the molecule, a compound represented by the following general formula (18) is preferable.

［一般式（１８）中、Ｅはｐ価の有機基を示し、ｐは１〜６の整数を示す。］

[In General Formula (18), E represents a p-valent organic group, and p represents an integer of 1 to 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.

  The resin compositions of the first and second embodiments described above may be applied directly to inorganic glass, or may be applied to inorganic glass after being formed into a film.

  Examples of the method for applying the resin composition include methods such as a dispensing method, a spin coating method, a die coating method, and a knife coating method, and are particularly suitable for application of a composition containing a high molecular weight compound. 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 resin layer 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.

<Transparent substrate>
For example, the transparent substrate of the present embodiment is a method of curing the resin layer after forming the resin layer on the inorganic glass by applying the resin composition described above, or by attaching a resin film on the inorganic glass. Examples include a method of curing the resin layer after forming the resin layer. Preferably, the resin layer is cured after the resin film is attached and the resin layer is formed on the inorganic glass. Such a method can be manufactured in a form suitable for the R2R (roll-to-roll) process, and a transparent substrate can be obtained at low cost.

  The method of forming a resin layer on the inorganic glass by the pasting step to obtain a transparent substrate is preferably a step of heating and pressing the resin film on one side or both sides of the inorganic glass, and heating the resin film after pasting Alternatively, it includes a curing step of curing the resin layer by 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 curing temperature is typically 120 to 220 ° C., and the curing time is typically 20 to 180 minutes.

  Next, an example of a process for producing a 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 mass based on the total mass, more preferably 0.01 to 2% by mass based on the total mass from the viewpoint of heat resistance reliability, and 0.01 to 1.5% by mass based on the total mass. 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. 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 performed 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).

  The thickness of the resin film is preferably 0.1 to 700 μm in order to prevent cracking of the substrate. If the thickness is less than 0.1 μm, the stress relaxation effect and the total light transmittance tend to be low. If the thickness is more than 700 μm, it is not economical and may not be able to meet the demand for weight reduction. In addition, 1-70 micrometers is more preferable at the point which has a stress relaxation effect and can make a board | substrate thin, More preferably, it is 5-50 micrometers.

(4) Vacuum lamination The resin film obtained in (3) is attached to inorganic glass. The method for attaching is not particularly limited as long as the resin film can be uniformly attached 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 less than 40 ° C. or the pressure is less than 0.2 MPa, the resin may not adhere to the glass layer, and if the temperature is higher than 120 ° C., the resin may be denatured. In addition, when the pressure exceeds 1.5 MPa, the glass may break.

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

(6) Fabrication of electrode IZO is sputtered on the transparent substrate obtained in (5) by vacuum deposition.

(7) Production of EL device An organic EL device is formed on the substrate obtained in (6), and the upper layer is sealed with cavity glass to obtain an organic EL device.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

(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. This was designated as f-1.

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

In addition, the component of Table 1 shows the following component specifically.
<(A) Acrylic polymer having a weight average molecular weight of 100,000 or more>
F-1 synthesized in the above (Synthesis of acrylic polymer 1)
<(B) Compound having at least two (meth) acryloyl groups>
<(A ′) Compound having at least two ethylenically unsaturated groups>
UN-952: Negami Kogyo Co., Ltd. (trade name), chemical name; 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 type dimethacrylate A-DOG: Shin-Nakamura Chemical Co., Ltd. (trade name), chemical substance name: dioxane glycol di Acrylate <(c) Polymerization initiator>
<(B ′) Thermal polymerization initiator>
Park Mill D: NOF Corporation (trade name) chemical name; Dicumyl peroxide, 1 hour half-life temperature 135.7 ° C, 10 hour half-life temperature 116.4 ° C
<(C ′) Hindered Phenol Compound>
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)
<(D ′) Thioether compound>
AO-412S: manufactured by ADEKA Corporation (trade name), thioether-based antioxidant, chemical name; bis [3- (dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxo Propyloxy] methyl] -1,3-propanediyl AO-503: manufactured by ADEKA Corporation (trade name), thioether-based antioxidant, chemical name; ditridecyl 3,3-thiobispropionate <(e ′) Compound having thiol group>
Karenz MT NR1: Showa Denko K.K. (trade name), chemical name; 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione <organic solvent>
PGMEA: manufactured by Kanto Chemical Co., Ltd., chemical name; propylene glycol 1-monomethyl ether 2-acetate; DMAc: Kanto Chemical Co., Ltd., chemical name; dimethylacetamide <other additives>
<Silane coupling agent>
KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd. (trade name), silane coupling agent, chemical substance name; 3-methacryloxypropylmethyldiethoxysilane, 3- (trimethoxysilyl) propyl methacrylate <others>
-HTR360P-3CSP: Chemical name of Nagase ChemteX Corporation (trade name); acrylic rubber Mw = approximately 800,000
YDCF-8170: manufactured by Tohto Kasei Co., Ltd. (trade name), chemical name; cresol novolac type epoxy resin 2Pz-CN: manufactured by Shikoku Kasei Kogyo Co., Ltd. (trade name), imidazole curing accelerator (1-cyanoethyl- 2-phenylimidazole)

Example 1
One side surface of inorganic glass (OA, manufactured by Nippon Electric Glass Co., Ltd.) having a thickness of 50 μm, a length of 100 mm, and a width of 100 mm was washed with N ₂ blow, and a resin having a length of 130 mm and a width of 130 mm under the conditions of 0.5 MPa, 65 ° C. and 60 s. Film A 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 B was used in place of the resin film A.

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

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

(Comparative Example 3)
A glass film OA-10G manufactured by Nippon Electric Glass Co., Ltd. having a thickness of 50 μm was used as a transparent substrate without using a resin film.

(Comparative Example 4)
Without using a resin film, an alkali-free glass plate FT-2K manufactured by Fuji Rika Kogyo Co., Ltd. having a thickness of 700 μm was used as a transparent substrate.

  The following tests were performed on the substrates of the examples and comparative examples (transparent substrates). The results are shown in Table 2.

(Peel strength measurement)
A 10 μm-thick resin film was vacuum-laminated on a glass film at 60 ° C., and a peel strength of a sample heat-cured at 120 ° C. for 1 hour was measured using an adhesion tester (manufactured by Hitachi Chemical Technoplant Co., Ltd.). The members used and the measurement conditions are shown below.
Film size: length 5.0mm, width 5.0mm, thickness 10μm
Glass film size: 20 mm long, 10 mm wide, 50 μm thick
Peel strength measurement speed: 0.5 mm / sec

(Bending test)
A transparent substrate having a length of 5 cm and a width of 5 cm was wound around a 3 cm diameter cylinder (SUS property). The test was performed 5 times, and the number of tests was shown in the numerator, and the number of times that the cracks could not be generated or wound was shown in the numerator.

(5% mass loss temperature test)
The mass reduction temperature (Td 5%) was measured by Tg / DTA. Temperature increase rate: 5 ° C / min

(Substrate weight measurement (weight per unit area))
The weight of the 1 cm ² transparent substrate was measured with a weigh scale.

(Flexural modulus)
The substrate (5 cm square) was measured with a three-point bending apparatus (manufactured by Shimadzu Corporation, model AUTOGRAPH AGS-X) under the condition of a width of 8 mm. Speed: 5mm / min

(Haze and total light transmittance)
It measured using the haze meter (Nippon Denshoku Industries Co., Ltd. product name "NDH5000W").

(Measurement of yellowness (YI value))
It measured using the chromaticity measuring device (Nippon Denshoku Industries Co., Ltd. product name "300A"). The yellowness was measured before curing and after curing at 200 ° C. for 120 minutes (2 hours).

(Organic EL emission test)
“○” indicates that the light emission can be confirmed visually when an organic EL element manufactured using each transparent substrate is applied with 5 V, “Δ” indicates that the light emission can be confirmed but there is unevenness, and “ “×” was evaluated.

(Organic EL device reliability test)
The produced organic EL device was put into a high temperature and humidity chamber at 85 ° C. and humidity 85% RH, and when it was applied with voltage of 5 V after 100 hours, “○” indicates that light emission can be visually confirmed, and “X” indicates the others. As evaluated.

In the epoxy resin film of Comparative Example 2, the total light transmittance is low, the haze is high, and the organic EL element cannot emit light. Further, the resin layer obtained by removing the components (c ′), (d ′), and (e ′) from the resin composition according to the second embodiment of the present invention has a high degree of yellowing after heating, and unevenness in light emission of the organic EL element. It was observed. In contrast, the resin layer of the present invention has a total light transmittance of 80% or more, a haze of 2.0% or less, a yellowness (YI value) of 6.0 or less, and a mass per unit area of 0.2 g / cm. ^In the transparent substrates of Examples 1 and ² which are ² or less, the EL element can emit light. Further, the light emission and light emission retention of the organic EL element when using the glass film of Comparative Example 3 having a thickness of 50 μm and the glass plate of Comparative Example 4 having a thickness of 700 μm are equivalent, and are lighter than Comparative Example 4. .

  DESCRIPTION OF SYMBOLS 1 ... Inorganic glass, 3, 3a, 3b ... Resin layer (resin cured material layer) 10, 20, 30, 40, 50 ... Transparent substrate.

Claims (7)

A transparent substrate comprising inorganic glass and a resin layer formed on at least one main surface of the inorganic glass, wherein the resin layer is heated at 180 ° C. for 120 minutes. The light transmittance is 80% or more, the haze of the resin layer after heating under the above conditions is 2.0% or less, the yellowness of the resin layer after heating the resin layer at 200 ° C. for 120 minutes ( A transparent substrate having a YI value of 6.0 or less and a mass per unit area of the transparent substrate of 0.2 g / cm ² or less.   The transparent substrate according to claim 1, wherein a 5% mass reduction temperature of the resin layer is 150 ° C or higher.   The transparent substrate according to claim 1 or 2, wherein a peel strength between the resin layer and the inorganic glass is 50 N / m or more.   The transparent substrate as described in any one of Claims 1-3 whose bending elastic modulus (25 degreeC) of the 2 layer structure which consists of an inorganic glass and a resin layer is 0.01-80GPa.   A resin composition in which the resin layer 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. The structural unit having a nitrogen atom-containing group in the acrylic polymer of the component (a) is 5% by mass or less of the whole acrylic polymer, and the component (a) is a structural unit having a functional group. The transparent substrate as described in any one of Claims 1-4 which is a hardened | cured material of the resin composition to contain.   The 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, and It is a hardened | cured material of the resin composition containing the compound which has (e ') thiol group, The transparent substrate as described in any one of Claims 1-4.   The transparent substrate according to claim 6, wherein the component (a ′) contains a urethane compound having a (meth) acryloyl group.

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