JP6683204B2 - Sealing resin composition - Google Patents

Description

  The present invention relates to a sealing resin composition, and particularly to a sealing resin composition that can be suitably used for sealing an organic EL element and the like.

  An organic EL (Electroluminescence) element is a light-emitting element that uses an organic substance as a light-emitting material, and is a material that has recently been in the spotlight because it can emit light with high brightness at low voltage. However, the organic EL element is extremely vulnerable to moisture, and the organic material itself deteriorates due to moisture, resulting in a decrease in brightness, no emission of light, peeling of the interface between the electrode and the organic EL layer due to moisture, and metal. However, there was a problem that it was oxidized and the resistance was increased.

  When the thermosetting resin composition is used as the entire surface encapsulating material, it is easy to laminate because the material viscosity before curing is low, and the moisture resistance of the cured product after thermosetting is high. To be However, on the other hand, there is a problem that the organic EL element deteriorates due to the heating temperature during thermosetting. Further, in the conventional can sealing structure, since the light is blocked by the getter agent layer incorporated in the sealing space for the purpose of dehydration, there is a drawback that the efficiency of extracting light from the sealing surface side is poor. The structure in which the entire surface is sealed with an object has an advantage that light emission from the sealing surface side can be efficiently extracted.

  As a sealing material suitable for avoiding the problem of heat deterioration of electronic parts such as organic EL devices, a resin composition containing a polyolefin such as polyisobutylene or a polyolefin-based copolymer and a tackifier Are known. Further, it is known that a hygroscopic metal oxide is blended with a sealing resin composition in order to improve moisture permeability (for example, Patent Documents 1 and 2).

International publication 2011/62167 International Publication 2013/108731

  When a hygroscopic metal oxide is added to a resin composition for encapsulation containing a polyolefin-based resin in order to improve the moisture resistance, there is a problem that transparency is lowered. Therefore, an object of the present invention is to provide a resin composition for encapsulation which has good moisture permeation resistance and transparency while using a polyolefin resin which can avoid the problem of heat deterioration.

  As a result of intensive studies by the present inventors, they have found that the above object can be achieved by adding a specific metal hydroxide to a polyolefin resin. The present invention based on this finding is as follows.

  [1] A sealing resin composition containing (A) a polyolefin resin and (B) a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite.

[2] The resin composition according to the above [1], wherein the (A) polyolefin-based resin contains a polyolefin-based resin having an acid anhydride group and / or a polyolefin-based resin having an epoxy group.
[3] The resin composition according to the above [2], wherein the amount of the polyolefin resin having an acid anhydride group in the (A) polyolefin resin is 0 to 70% by mass.
[4] The resin composition according to the above [2] or [3], wherein the amount of the polyolefin resin having an epoxy group in the (A) polyolefin resin is 0 to 70% by mass.

[5] The resin composition according to the above [1], in which the (A) polyolefin-based resin contains a polyolefin-based resin having an acid anhydride group and a polyolefin-based resin having an epoxy group.
[6] The resin composition according to [5], wherein the amount of the polyolefin resin having an acid anhydride group in the polyolefin resin (A) is 10 to 50% by mass.
[7] The resin composition according to the above [5] or [6], wherein the amount of the polyolefin resin having an epoxy group in the polyolefin resin (A) is 10 to 50% by mass.

[8] The molar ratio (epoxy group: acid anhydride group) between the epoxy group of the polyolefin resin having an epoxy group and the acid anhydride group of the polyolefin resin having an acid anhydride group is 100: 10 to 100: The resin composition according to any one of [5] to [7], which is 200.
[9] The molar ratio of the epoxy group of the polyolefin resin having an epoxy group to the acid anhydride group of the polyolefin resin having an acid anhydride group (epoxy group: acid anhydride group) is 100: 50 to 100: The resin composition according to any one of the above [5] to [7], which is 150.
[10] The molar ratio (epoxy group: acid anhydride group) of the epoxy group of the polyolefin resin having an epoxy group and the acid anhydride group of the polyolefin resin having an acid anhydride group is 100: 90 to 100: 110. The resin composition according to any one of [5] to [7], which is 110.

[11] The resin composition according to any one of [2] to [10], wherein the acid anhydride group-containing polyolefin resin has a concentration of acid anhydride groups of 0.05 to 10 mmol / g. .
[12] The resin composition according to any one of [2] to [10], wherein the concentration of the acid anhydride group in the polyolefin resin having an acid anhydride group is 0.1 to 5 mmol / g. .

[13] The resin composition according to any one of [2] to [12], wherein the concentration of the epoxy group in the polyolefin resin having an epoxy group is 0.05 to 10 mmol / g.
[14] The resin composition according to any one of [2] to [12], wherein the concentration of the epoxy group in the polyolefin resin having an epoxy group is 0.1 to 5 mmol / g.

[15] The resin composition according to any one of the above [1] to [14], wherein the number average molecular weight of the (A) polyolefin resin is 1,000,000 or less.
[16] The resin composition according to any one of the above [1] to [14], wherein the polyolefin resin (A) has a number average molecular weight of 750,000 or less.
[17] The resin composition according to any one of the above [1] to [14], wherein the polyolefin resin (A) has a number average molecular weight of 500,000 or less.
[18] The resin composition according to any one of the above [1] to [14], wherein the polyolefin resin (A) has a number average molecular weight of 400,000 or less.
[19] The resin composition according to any one of the above [1] to [14], wherein the (A) polyolefin resin has a number average molecular weight of 300,000 or less.
[20] The resin composition according to any one of the above [1] to [14], wherein the polyolefin resin (A) has a number average molecular weight of 200,000 or less.
[21] The resin composition according to any one of the above [1] to [14], wherein the polyolefin resin (A) has a number average molecular weight of 150,000 or less.

[22] The resin composition according to any one of the above [1] to [21], wherein the (A) polyolefin resin has a number average molecular weight of 1,000 or more.
[23] The resin composition according to any one of the above [1] to [21], wherein the (A) polyolefin resin has a number average molecular weight of 3,000 or more.
[24] The resin composition according to any one of the above [1] to [21], wherein the (A) polyolefin resin has a number average molecular weight of 5,000 or more.
[25] The resin composition according to any one of the above [1] to [21], wherein the (A) polyolefin resin has a number average molecular weight of 10,000 or more.
[26] The resin composition according to any one of the above [1] to [21], wherein the (A) polyolefin resin has a number average molecular weight of 30,000 or more.
[27] The resin composition according to any one of the above [1] to [21], wherein the polyolefin resin (A) has a number average molecular weight of 50,000 or more.

[28] The content of the (A) polyolefin-based resin is 80% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [27]. Resin composition.
[29] The content of the (A) polyolefin-based resin is 75% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [27]. Resin composition.
[30] The content of the (A) polyolefin-based resin is 70% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [27]. Resin composition.
[31] The content of the (A) polyolefin-based resin is 60% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [27]. Resin composition.
[32] The content of the (A) polyolefin-based resin is 55% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [27]. Resin composition.
[33] The content of the (A) polyolefin-based resin is 50% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [27]. Resin composition.

[34] The content of the polyolefin resin (A) is 1% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [33]. Resin composition.
[35] The content of the (A) polyolefin-based resin is 3% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [33]. Resin composition.
[36] The content of the (A) polyolefin-based resin is 5% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [33]. Resin composition.
[37] The content of the (A) polyolefin-based resin is 7% by mass or more based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [33]. Resin composition.
[38] The content of the (A) polyolefin-based resin is 10% by mass or more per 100% by mass of the total non-volatile content in the resin composition, according to any one of the above [1] to [33]. Resin composition.
[39] The content of the polyolefin resin (A) is 35% by mass or more based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [33]. Resin composition.
[40] The content of the (A) polyolefin-based resin is 40% by mass or more based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [33]. Resin composition.

  [41] The metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite is the calcined hydrotalcite as described in any one of [1] to [40] above. Resin composition.

[42] Any one of the above-mentioned [1] to [41], wherein the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite has a BET specific surface area of 1 to 200 m ² / g. The resin composition according to one.
[43] (B) Any of the above-mentioned [1] to [41], wherein the metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite has a BET specific surface area of 5 to 150 m ² / g. The resin composition according to one.

[44] (B) In any one of the above [1] to [43], wherein the metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite has an average particle diameter of 1 to 1000 nm. The resin composition described.
[45] In any one of the above [1] to [43], the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite has an average particle diameter of 10 to 500 nm. The resin composition described.

[46] The content of the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite is 60 mass% or less per 100 mass% of the total nonvolatile content in the resin composition. The resin composition according to any one of [1] to [45].
[47] The content of the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite is 55 mass% or less per 100 mass% of the total nonvolatile content in the resin composition. The resin composition according to any one of [1] to [45].
[48] The content of the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite is 50% by mass or less per 100% by mass of the total nonvolatile content in the resin composition. The resin composition according to any one of [1] to [45].
[49] The content of the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite is 45% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition. The resin composition according to any one of [1] to [45].

[50] The content of the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite is 10% by mass or more per 100% by mass of the total nonvolatile content in the resin composition. The resin composition according to any one of [1] to [49].
[51] The content of the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite is 20% by mass or more per 100% by mass of the total nonvolatile content in the resin composition. The resin composition according to any one of [1] to [49].
[52] The content of the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite is 30% by mass or more based on 100% by mass of the total nonvolatile content in the resin composition. The resin composition according to any one of [1] to [49].

  [53] The resin composition according to any one of [1] to [52], further including (C) a tackifying resin.

[54] The resin composition according to the above [53], wherein the tackifying resin (C) has a softening point of 50 to 200 ° C.
[55] The resin composition according to the above [53], wherein the tackifying resin (C) has a softening point of 90 to 180 ° C.
[56] The resin composition according to the above [53], wherein the tackifying resin (C) has a softening point of 100 to 150 ° C.

[57] The content of the tackifying resin (C) according to any one of the above [53] to [56], which is 80% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition. Resin composition.
[58] The content of the tackifying resin (C) according to any one of the above [53] to [56], which is 60% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition. Resin composition.
[59] The content of the tackifying resin (C) according to any one of the above [53] to [56], which is 50% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition. Resin composition.
[60] The content of the tackifying resin (C) is 40% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [53] to [56]. Resin composition.

[61] The content of the tackifying resin (C) according to any one of the above [53] to [60], which is 5% by mass or more per 100% by mass of the total nonvolatile content in the resin composition. Resin composition.
[62] The content of the tackifying resin (C) according to any one of the above [53] to [60], which is 10% by mass or more per 100% by mass of the total nonvolatile content in the resin composition. Resin composition.
[63] The content of the tackifying resin (C) according to any one of the above [53] to [60], which is 15% by mass or more based on 100% by mass of the total nonvolatile content in the resin composition. Resin composition.

  [64] The resin composition according to any one of [1] to [63], further including (D) a curing agent.

[65] The resin composition according to the above [64], wherein the content of the (D) curing agent is 5% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition.
[66] The resin composition according to the above [64], wherein the content of the (D) curing agent is 1% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition.

[67] The content of the curing agent (D) is 0.01% by mass or more based on 100% by mass of the total non-volatile components in the resin composition, according to any one of the above [64] to [66]. Resin composition.
[68] The content of the (D) curing agent is 0.05% by mass or more based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [64] to [66]. Resin composition.

[69] The resin according to any one of the above [1] to [68], wherein the content of the hygroscopic metal oxide is 1% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition. Composition.
[70] The content of the hygroscopic metal oxide is 0.5% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [68]. Resin composition.

[71] The resin composition according to any one of [1] to [70], which is a pressure-sensitive adhesive.
[72] The resin composition according to any one of [1] to [71], which is used for sealing an organic EL element.

[73] The total light transmittance (parallel light transmittance) at a wavelength of 450 nm of the resin composition layer having a thickness of 20 μm is 90% or more, and the resin composition layer is described in any one of the above [1] to [72]. Resin composition.
[74] The total light transmittance (parallel transmittance) at a wavelength of 450 nm of the resin composition layer having a thickness of 20 μm is 95% or more, and the resin composition layer according to any one of the above [1] to [72]. Resin composition.

[75] A sealing sheet in which a resin composition layer comprising the resin composition according to any one of [1] to [74] is formed on one side or both sides of a support.
[76] (A) The polyolefin-based resin contains a polyolefin-based resin having an acid anhydride group and a polyolefin-based resin having an epoxy group, and the resin composition layer has a crosslinked structure in which an acid anhydride group and an epoxy group are reacted. The encapsulating sheet according to the above [75].
[77] The encapsulating sheet according to the above [75] or [76] for encapsulating an organic EL element.

[78] An organic EL device having an organic EL element sealed with the resin composition according to any one of [1] to [74].
[79] An organic EL device having an organic EL element sealed with the sealing sheet according to any one of [75] to [77].

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the sealing composition which uses the polyolefin resin which can avoid the problem of heat deterioration, and has the characteristics of both favorable moisture-proof property and transparency.

  The encapsulating resin composition of the present invention is selected from the group consisting of (A) a polyolefin resin (hereinafter sometimes abbreviated as “(A) component”), and (B) hydrotalcite and semi-calcined hydrotalcite. It is characterized by containing a selected metal hydroxide (hereinafter sometimes abbreviated as “(B) component”).

  From the encapsulating resin composition of the present invention, an encapsulating layer (resin composition layer) having good moisture resistance and transparency can be formed. This transparency can be judged by the total light transmittance (parallel line transmittance) of the resin composition layer. The total light transmittance (parallel light transmittance) at a wavelength of 450 nm of the resin composition layer having a thickness of 20 μm is preferably 90% or more, and more preferably 95% or more. This total light transmittance is calculated by using glass as a reference, as described in Examples described later.

<(A) Polyolefin resin>
The polyolefin resin used in the present invention is not particularly limited as long as it has a skeleton derived from an olefin monomer. For example, the polyolefin-based resins described in Patent Documents 1 and 2 are known. The polyolefin resin is preferably a polyethylene resin, a polypropylene resin, a polybutene resin, or a polyisobutylene resin. These polyolefin resins may be homopolymers or copolymers such as random copolymers and block copolymers. Examples of the copolymer include copolymers of two or more kinds of olefins, and copolymers of olefins with monomers other than olefins such as non-conjugated dienes and styrene. Examples of preferred copolymers include ethylene-non-conjugated diene copolymers, ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene copolymers, ethylene-butene copolymers, propylene-butene copolymers, propylene. -Butene-non-conjugated diene copolymer, styrene-isobutylene copolymer, styrene-isobutylene-styrene copolymer and the like. As the polyolefin-based resin, for example, the isobutylene-modified resin described in Patent Document 1 and the styrene-isobutylene-modified resin described in Patent Document 2 are preferably used.

  The polyolefin resin (A) is a polyolefin resin having an acid anhydride group (that is, a carbonyloxycarbonyl group (—CO—O—CO—)) from the viewpoint of imparting excellent physical properties such as adhesiveness and adhesion wet heat resistance. It is preferable to include a resin and / or a polyolefin resin having an epoxy group. Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride, and the like. The acid anhydride group can have 1 type (s) or 2 or more types. The polyolefin resin having an acid anhydride group is obtained, for example, by graft-modifying the polyolefin resin with an unsaturated compound having an acid anhydride group under radical reaction conditions. Further, the unsaturated compound having an acid anhydride group may be radically copolymerized with an olefin or the like. Similarly, the polyolefin resin having an epoxy group is, for example, an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether. It is obtained by graft modification with. Further, an unsaturated compound having an epoxy group may be radically copolymerized with an olefin or the like. As the component (A), one type or two or more types can be used, and a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group may be used in combination.

  The concentration of the acid anhydride group in the polyolefin resin having an acid anhydride group is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g. The concentration of the acid anhydride group is obtained from the value of the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the resin, according to the description of JIS K 2501. Moreover, the amount of the polyolefin resin having an acid anhydride group in the component (A) is preferably 0 to 70% by mass, and more preferably 10 to 50% by mass.

  Further, the concentration of the epoxy group in the polyolefin resin having an epoxy group is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g. The epoxy group concentration is determined from the epoxy equivalent obtained according to JIS K 7236-1995. The amount of the epoxy group-containing polyolefin resin in the component (A) is preferably 0 to 70% by mass, more preferably 10 to 50% by mass.

  The polyolefin resin (A) preferably contains both a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group, from the viewpoint of imparting excellent physical properties such as moisture resistance. Such a polyolefin resin can form a cross-linked structure by reacting an acid anhydride group with an epoxy group by heating to form a sealing layer having excellent moisture resistance and the like. The crosslinked structure can be formed after sealing, but when the sealing target is one that is weak to heat, such as an organic EL element, when sealing is performed using a sealing film, the sealing film is produced. It is desirable to form a crosslinked structure. The ratio of the polyolefin resin having an acid anhydride group and the polyolefin resin having an epoxy group is not particularly limited as long as a suitable crosslinked structure can be formed, but the molar ratio of the epoxy group and the acid anhydride group (epoxy group: acid anhydride The group) is preferably 100: 10 to 100: 200, more preferably 100: 50 to 100: 150, and particularly preferably 100: 90 to 100: 110.

  The number average molecular weight of the (A) polyolefin resin is not particularly limited, but from the viewpoint of providing good coatability of the varnish of the resin composition and good compatibility with other components in the resin composition, 1 1,000,000 or less is preferred, 750,000 or less is more preferred, 500,000 or less is even more preferred, 400,000 or less is still more preferred, 300,000 or less is even more preferred, 200,000 or less is particularly preferred, Most preferably, it is 150,000 or less. On the other hand, from the viewpoint of preventing cissing at the time of applying a varnish of the resin composition, developing moisture resistance of the formed resin composition layer, and improving mechanical strength, the number average molecular weight is 1,000. The above is preferable, 3,000 or more is more preferable, 5,000 or more is still more preferable, 10,000 or more is further preferable, 30,000 or more is still more preferable, 50,000 or more is particularly preferable. The number average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (polystyrene conversion). The number average molecular weight measured by the GPC method is, specifically, LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column. It can be calculated by using toluene or the like as a phase at a column temperature of 40 ° C. and using a calibration curve of standard polystyrene.

  The polyolefin resin (A) in the present invention is preferably amorphous from the viewpoint of suppressing a decrease in fluidity due to thickening of the varnish. Here, the term "amorphous" means that the polyolefin resin does not have a definite melting point, and for example, a definite peak is not observed when the melting point is measured by DSC (differential scanning calorimetry) of the polyolefin resin. Things can be used.

  The content of the component (A) in the resin composition of the present invention is not particularly limited. However, from the viewpoint of providing good coatability and compatibility, and ensuring good wet heat resistance and handleability (tack suppression), the content is 100% by mass of the total nonvolatile content in the resin composition, 80 mass% or less is preferable, 75 mass% or less is more preferable, 70 mass% or less is still more preferable, 60 mass% or less is still more preferable, 55 mass% or less is still more preferable, and 50 mass% or less is especially preferable. On the other hand, the content is preferably 1% by mass or more and more preferably 3% by mass or more per 100% by mass of the total non-volatile content in the resin composition from the viewpoint of improving moisture permeability resistance and improving transparency. It is more preferably 5 mass% or more, still more preferably 7 mass% or more, still more preferably 10 mass% or more, particularly preferably 35 mass% or more, and most preferably 40 mass% or more.

  Next, a specific example of the (A) polyolefin resin will be described. Specific examples of the polyisobutylene resin include "Opanol B100" (viscosity average molecular weight: 1,110,000) manufactured by BASF and "B50SF" (viscosity average molecular weight: 400,000) manufactured by BASF.

  Specific examples of the polybutene-based resin include "HV-1900" (polybutene, number average molecular weight: 2,900) manufactured by JX Energy Co., Ltd., "HV-300M" (maleic anhydride-modified liquid polybutene ("HV" manufactured by Toho Chemical Industry Co., Ltd.). -300 "(modified product of number average molecular weight: 1,400), number average molecular weight: 2,100, number of carboxy groups constituting an acid anhydride group: 3.2 per molecule, acid value: 43. 4 mgKOH / g, acid anhydride group concentration: 0.77 mmol / g).

  Specific examples of the styrene-isobutylene copolymer include "SIBSTAR T102" (styrene-isobutylene-styrene block copolymer, number average molecular weight: 100,000, styrene content: 30 mass%) manufactured by Kaneka Corporation, manufactured by Starlight PMC. "T-YP756B" (maleic anhydride-modified styrene-isobutylene-styrene block copolymer, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 100,000), "T-YP766" manufactured by Seikou PMC Co., Ltd. (Glycidyl methacrylate modified styrene-isobutylene-styrene block copolymer, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 100,000), "T-YP8920" manufactured by Starlight PMC (maleic anhydride modified styrene-isobutylene) -Styrene copolymer, acid anhydride group concentration 0.464 mmol / g, number average molecular weight: 35,800), "T-YP8930" (Glycidyl methacrylate modified styrene-isobutylene-styrene copolymer, manufactured by Seikou PMC, epoxy group concentration: 0.638 mmol / g, number average molecular weight : 48,700).

  Specific examples of the polyethylene-based resin or polypropylene-based resin include "EPT X-3012P" (ethylene-propylene-5-ethylidene-2-norbornene copolymer manufactured by Mitsui Chemicals, Inc., "EPT1070" (ethylene-propylene manufactured by Mitsui Chemicals, Inc.). -Dicyclopentadiene copolymer) and "Tufmer A4085" (ethylene-butene copolymer) manufactured by Mitsui Chemicals, Inc.

  Specific examples of the propylene-butene-based copolymer include "T-YP341" manufactured by Seikou PMC (glycidyl methacrylate-modified propylene-butene random copolymer, the amount of butene units per 100 mass% of the total of propylene units and butene units). : 29% by mass, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 155,000, "T-YP279" manufactured by Seikou PMC (maleic anhydride-modified propylene-butene random copolymer, propylene unit and butene) Amount of butene units per total 100 mass% of units: 36 mass%, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 35,000, "T-YP276" (Glycidyl methacrylate) manufactured by Starlight PMC. Modified propylene-butene random copolymer, total of propylene unit and butene unit 1 Amount of butene unit per 0% by mass: 36% by mass, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 57,000), "T-YP312" manufactured by Seikou PMC (maleic anhydride-modified propylene-butene) Random copolymer, amount of butene units per total 100% by weight of propylene units and butene units: 29% by weight, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 60,900), Starlight PMC "T-YP313" (glycidyl methacrylate modified propylene-butene random copolymer, amount of butene units per total 100% by weight of propylene units and butene units: 29% by weight, epoxy group concentration: 0.638 mmol / g, Number average molecular weight: 155,000, "T-YP429" manufactured by Hoshiko PMC (maleic anhydride modified ethylene Methyl methacrylate copolymer, amount of methyl methacrylate unit per total 100 mass% of ethylene unit and methyl methacrylate unit: 32 mass%, acid anhydride group concentration: 0.46 mmol / g, number average molecular weight: 2,300), Star light PMC "T-YP430" (maleic anhydride-modified ethylene-methylmethacrylate copolymer, the amount of methylmethacrylate units per 100% by weight of total ethylene units and methylmethacrylate units: 32% by weight, acid anhydride group concentration : 1.18 mmol / g, number average molecular weight: 4,500), "T-YP431" manufactured by Seikou PMC (glycidyl methacrylate modified ethylene-methyl methacrylate copolymer, epoxy group concentration: 0.64 mmol / g, number average molecular weight : 2,400), "T-YP432" manufactured by Hoshiko PMC Ltd. (Glycidyl methacrylate modified ethylene-methyl methacrylate copolymer, epoxy group concentration: 1.63 mmol / g, number average molecular weight: 3,100).

<(B) Metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite>
"Hydrotalcite" in the present invention is a concept including natural hydrotalcite uncalcined _{(Mg 6 Al 2 (OH)} 16 CO 3 · 4H 2 O) and synthetic hydrotalcite (hydrotalcite-like compound) is there. That is, the "hydrotalcite" in the present invention means "unbaked hydrotalcite".

From the viewpoint of hygroscopicity, semi-calcined hydrotalcite is preferable as the component (B). That is, it is preferable that the metal hydroxide comprises semi-calcined hydrotalcite. The term "semi-calcined hydrotalcite" as used herein means that the amount of interlayer water obtained by calcining hydrotalcite (that is, natural hydrotalcite or synthetic hydrotalcite (hydrotalcite-like compound)) decreases or disappears. Referred to as a metal hydroxide. The “interlayer water” refers to “H ₂ O” described in the composition formula of the above-mentioned natural hydrotalcite and the synthetic hydrotalcite (hydrotalcite-like compound) described below, if it is explained using the composition formula.

  Calcination of hydrotalcite (that is, natural hydrotalcite or synthetic hydrotalcite (hydrotalcite-like compound)) or semi-calcined hydrotalcite obtained by calcining not only interlayer water but also hydroxyl groups by condensation dehydration Hydrotalcite is a metal oxide and is not included in the component (B) of the present invention (that is, hydrotalcite and / or semi-calcined hydrotalcite) which is a metal hydroxide. In addition, hydrotalcite and semi-calcined hydrotalcite have peaks observed in their TG-DTA (Thermogravimetry-Differential Thermal Analysis) curves, but calcined hydrotalcite becomes amorphous due to disappearance of hydroxyl groups, No peak is observed on the TG-DTA curve. Therefore, hydrotalcite and semi-calcined hydrotalcite and calcined hydrotalcite can be clearly distinguished by TG-DTA.

  Further, hydrotalcite and semi-calcined hydrotalcite can be distinguished from calcined hydrotalcite by the thermogravimetric reduction rate measured by thermogravimetric analysis. The thermal weight loss rate of the semi-calcined hydrotalcite at 280 ° C is less than 15% by mass, and the thermal weight loss rate at 380 ° C is 12% by mass or more. On the other hand, the thermal weight loss rate of hydrotalcite at 280 ° C is 15% by mass or more, and the thermal weight loss rate of calcined hydrotalcite at 380 ° C is less than 12% by weight.

Thermogravimetric analysis was performed using Hitachi High-Tech Science Co., Ltd. TG / DTA EXSTAR6300, 5 mg of hydrotalcite was weighed in a sample pan made of AL, in an open state without a lid, under an atmosphere of nitrogen flow rate of 200 mL / min, It can be performed at a temperature rising rate of 10 ° C./min from 30 ° C. to 550 ° C. The thermal weight loss rate is the following formula:
Thermal weight loss rate (mass%)
= 100 × (mass before heating−mass when reaching a predetermined temperature) / mass before heating.

  Further, hydrotalcite and semi-calcined hydrotalcite can be distinguished from calcined hydrotalcite by the peak and the relative intensity ratio measured by powder X-ray diffraction. Semi-calcined hydrotalcite shows a peak split by 2 in the vicinity of 8 to 18 ° by powder X-ray diffraction, or a peak having a shoulder due to the synthesis of the two peaks, and a peak or shoulder appearing on the low angle side. The relative intensity ratio (low-angle side diffraction intensity / high-angle side diffraction intensity) between the diffraction intensity (= low-angle side diffraction intensity) and the peak or shoulder diffraction intensity (= high-angle side diffraction intensity) appearing on the high-angle side is 0.001. ~ 1,000. On the other hand, hydrotalcite has only one peak around 8 to 18 °, or the relative intensity ratio of the diffraction intensity of the peak or shoulder appearing on the low angle side and the peak or shoulder appearing on the high angle side is out of the above range. Become. Calcined hydrotalcite does not have a characteristic peak in the region of 8 ° to 18 °, but has a characteristic peak at 43 °. The powder X-ray diffraction measurement was performed using a powder X-ray diffractometer (PANalytical, Empyrean) with an anticathode CuKα (1.5405Å), voltage: 45 V, current: 40 mA, sampling width: 0.0260 °, scanning speed: 0. 0.0657 ° / S, and measurement diffraction angle range (2θ): 5.0131 to 79.9711 °. The peak search uses the peak search function of the software attached to the diffractometer, and "minimum significance: 0.50, minimum peak tip: 0.01 °, maximum peak tip: 1.00 °, peak base width: 2 "0.000, method: minimum value of second derivative".

  For example, in powder X-ray diffraction measurement under the above conditions, hydrotalcite "DHT-4A" manufactured by Kyowa Chemical Industry Co., Ltd. has one peak at 11.4 °. The semi-calcined hydrotalcite "DHT-4C" manufactured by Kyowa Chemical Industry Co., Ltd. has a main peak at 13.2 ° and a second peak at 11.4 °.

  Further, hydrotalcite and semi-calcined hydrotalcite can be distinguished from calcined hydrotalcite by the saturated water absorption. The saturated water absorption of the semi-calcined hydrotalcite is 1% by weight or more and less than 20% by weight. On the other hand, the saturated water absorption rate of hydrotalcite is less than 1% by weight, and the saturated water absorption rate of calcined hydrotalcite is 20% by weight or more.

The "saturated water absorption" in the present invention means that hydrotalcite, semi-calcined hydrotalcite or calcined hydrotalcite is weighed by a balance in an amount of 1.5 g, and the initial mass is measured. % RH (Relative Humidity) When set to a small environment tester (SH-222 manufactured by Espec Co., Ltd.) for 200 hours, it refers to the mass increase rate relative to the initial mass.
Saturated water absorption (% by mass)
= 100 × (mass after moisture absorption−initial mass) / initial mass.

Examples of the synthetic hydrotalcite (hydrotalcite-like compound) include compounds represented by the formula (I):
[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] ^{x +} · [(A ⁿ⁻ ) _{x / n} · mH ₂ O] ^x− (I)
(In the formula, M ²⁺ represents a divalent metal ion such as Mg ²⁺ and Zn ²⁺ , M ³⁺ represents a trivalent metal ion such as Al ³⁺ and Fe ³⁺ , and A ⁿ⁻ represents CO ₃ ²⁻ and Cl. ⁻ , NO ₃ ^−, and other n-valent anions, and 0 <x <1, 0 ≦ m <1, and n is a positive number. Wherein ^{(I), M 2+} is preferably ^{Mg 2+, M 3+} is preferably ^{Al 3+, A n-is} preferably _CO ^{3 2-.}

Further, as the synthetic hydrotalcite (hydrotalcite-like compound), for example, a compound represented by the formula (II):
M ²⁺ _x Al ₂ (OH) _{2x + 6-nz} (A ⁿ⁻ ) _z · mH ₂ O (II)
(In the formula, M ²⁺ represents a divalent metal ion such as Mg ²⁺ and Zn ²⁺ , A ⁿ⁻ represents an n-valent anion such as CO ₃ ²⁻ , Cl ⁻ , NO ₃ ⁻ , and x is 2 or more. Is a positive number, z is a positive number less than or equal to 2, m is a positive number, and n is a positive number.)
What is represented by. In formula (II), M ²⁺ is preferably Mg ²⁺ and A ⁿ⁻ is preferably CO ₃ ²⁻ .

(B) BET specific surface area of the component is preferably ^{1~200m 2 / g, 5~150m 2 /} g is more preferable. The BET specific surface area of the component (B) is determined according to the BET method by using a specific surface area measuring device (manufactured by Macsorb HM Model-1210 manufactured by Mountech Co., Ltd.) to adsorb nitrogen gas on the sample surface, and using the BET multipoint method. It is obtained by calculating.

  The average particle diameter of the component (B) is preferably 1 to 1000 nm, more preferably 10 to 500 nm. The average particle diameter of the component (B) is obtained as the median diameter of the particle size distribution when the particle size distribution is prepared on the volume basis by laser diffraction / scattering particle size distribution measurement (JIS Z 8825).

  As the component (B), those surface-treated with a surface treatment agent can be used. As the surface treatment agent used for the surface treatment, for example, higher fatty acids, alkylsilanes, silane coupling agents and the like can be used, and among them, higher fatty acids and alkylsilanes are preferable. As the surface treatment agent, one kind or two or more kinds can be used.

  Examples of the higher fatty acid include higher fatty acids having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid, and palmitic acid. Among them, stearic acid is preferable. These may be used alone or in combination of two or more. Examples of the alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, and n-octadecyldimethyl ( 3- (trimethoxysilyl) propyl) ammonium chloride and the like can be mentioned. These may be used alone or in combination of two or more. Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Epoxy-based silane coupling agents such as silane; mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrisilane Amino-based silane cups such as toxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Ring agent; ureido silane coupling agent such as 3-ureidopropyltriethoxysilane, vinyl silane coupling agent such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; p-styryltrimethoxysilane, etc. Styryl-based silane coupling agent; acrylate-based silane coupling agent such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; 3-isocyanatopropyltrimetho Isocyanate-based silane coupling agents such as silane, sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole Examples thereof include silane and triazine silane. These may be used alone or in combination of two or more.

  The surface treatment of the component (B) can be carried out, for example, by adding and spraying a surface treatment agent and stirring for 5 to 60 minutes while stirring and dispersing the untreated component (B) at room temperature with stirring. . As the mixer, a known mixer can be used, and examples thereof include a blender such as a V blender, a ribbon blender, and a bubble cone blender, a mixer such as a Henschel mixer and a concrete mixer, a ball mill, a cutter mill, and the like. In addition, when pulverizing the hygroscopic material with a ball mill or the like, a method of mixing the above-mentioned higher fatty acid, alkylsilanes or silane coupling agent and surface-treating is also possible. The treatment amount of the surface treatment agent varies depending on the type of the component (B) or the type of the surface treatment agent, but is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component (B).

  The content of the component (B) in the resin composition of the present invention is not particularly limited. However, from the viewpoint of maintaining the adhesion between the resin composition layer and a substrate such as glass and the transparency of the resin composition layer, the content is 60 mass per 100 mass% of the total nonvolatile content in the resin composition. % Or less, preferably 55% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less. Further, from the viewpoint of sufficiently obtaining the effect of hygroscopicity, the content is preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass with respect to 100% by mass of the total nonvolatile content in the resin composition. The above is more preferable.

Specific examples of the component (B) in the present invention include the following:
DHT-4C (manufactured by Kyowa Chemical Industry Co., Ltd.): Semi-calcined hydrotalcite (average particle diameter: 400 nm, BET specific surface area: 15 m ² / g)
DHT-4A-2 (manufactured by Kyowa Chemical Industry Co., Ltd.): Semi-calcined hydrotalcite (average particle diameter: 400 nm, BET specific surface area: 10 m ² / g)
DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.): Hydrotalcite (average particle size: 400 nm, BET specific surface area: 10 m ² / g)

<Hygroscopic metal oxide>
When a hygroscopic metal oxide is added to a resin composition containing a polyolefin resin, its transparency tends to decrease. Therefore, from the viewpoint of improving transparency, the resin composition of the present invention preferably contains substantially no hygroscopic metal oxide. The content of the hygroscopic metal oxide is, for example, preferably in a range such that the transmittance value of the resin composition layer described later is preferably 90% or more, more preferably 95% or more. For example, the content of the hygroscopic metal oxide is preferably 1% by mass or less (i.e., 0 to 1% by mass), and 0.5% by mass or less (i.e., 100% by mass) based on the total 100% by mass of the nonvolatile components in the resin composition. , 0 to 0.5 mass%) is more preferable. Examples of the hygroscopic metal oxide include calcium oxide, magnesium oxide, strontium oxide, aluminum oxide, barium oxide, calcined dolomite (mixture containing calcium oxide and magnesium oxide), calcined hydrotalcite.

<(C) Tackifying resin>
The resin composition of the present invention may further contain (C) a tackifying resin (hereinafter sometimes abbreviated as “(C) component”). The tackifying resin is also called a tackifier, and is a resin that is blended with a plastic polymer to impart tackiness. The component (C) is not particularly limited and includes terpene resins, modified terpene resins (hydrogenated terpene resins, terpene phenol copolymer resins, aromatic modified terpene resins, etc.), coumarone resins, indene resins, petroleum resins ( Aliphatic petroleum resin, hydrogenated alicyclic petroleum resin, aromatic petroleum resin, aliphatic aromatic copolymer petroleum resin, alicyclic petroleum resin, dicyclopentadiene petroleum resin and its hydride etc.) Preferably used.

  Examples of commercially available products that can be used as the component (C) include the following. Examples of the terpene resin include YS resin PX and YS resin PXN (both manufactured by Yasuhara Chemical Co., Ltd.), and aromatic modified terpene resins include YS resin TO and TR series (both manufactured by Yasuhara Chemical Co., Ltd.). The terpene resin includes Clearon P, Clearon M, Clearon K series (all manufactured by Yasuhara Chemical Co., Ltd.), and the terpene phenol copolymer resin is YS Polystar 2000, Polystar U, Polystar T, Polystar S, Mighty Ace G (any Yasuhara Chemical Co., Ltd.) and the like, hydrogenated alicyclic petroleum resins such as Escorez 5300 series, 5600 series (both manufactured by ExxonMobil) and the like, and ENDEX155 (Eastman Co.) as aromatic petroleum resin. Examples thereof include Quintone D100 (manufactured by Zeon Corporation) as the aliphatic aromatic copolymer-based petroleum resin, and Quintone 1325, Quintone 1345 (both manufactured by Nippon Zeon) as the alicyclic petroleum resin, and cyclohexane. Examples of the ring-containing hydrogenated petroleum resin include Alcon P100, Alcon P125, Alcon P140 (all manufactured by Arakawa Chemical Co., Ltd.) and the like, and examples of the cyclohexane ring-containing saturated hydrocarbon resin include TFS13-030 (manufactured by Arakawa Chemical Co., Ltd.).

  The softening point of the component (C) is preferably 50 to 200 ° C, more preferably 90 to 180 ° C, and more preferably 100 to 200, from the viewpoint that the sheet softens in the laminating step of the resin composition sheet and has desired heat resistance. 150 ° C. is more preferable. The softening point is measured by the ring and ball method according to JIS K2207.

  The component (C) may be used alone or in combination of two or more. The content of the component (C) in the resin composition is not particularly limited. However, from the viewpoint of maintaining good moisture permeation resistance of the resin composition, when the component (C) is used, its content is 80% by mass or less per 100% by mass of the total nonvolatile content in the resin composition. Is preferred, 60% by mass or less is more preferred, 50% by mass or less is more preferred, and 40% by mass or less is particularly preferred. On the other hand, from the viewpoint of having sufficient adhesiveness, when the component (C) is used, its content is preferably 5% by mass or more based on 100% by mass of the total nonvolatile content in the resin composition, and 10% by mass. The above is more preferable, and 15% by mass or more is further preferable.

Among them, petroleum resin is preferable from the viewpoint of adhesiveness, moisture permeability resistance, transparency, etc. of the resin composition. Examples of the petroleum resin include an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic aromatic copolymer petroleum resin, and an alicyclic petroleum resin. Among them, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, and alicyclic petroleum resins are more preferable from the viewpoint of adhesiveness, moisture permeability resistance, compatibility, etc. of the resin composition. From the viewpoint of improving transparency, alicyclic petroleum resin is particularly preferable. As the alicyclic petroleum resin, a hydrogenated aromatic petroleum resin may be used. In this case, the hydrogenation rate of the alicyclic petroleum resin is preferably 30 to 99%, more preferably 40 to 97%, even more preferably 50 to 90%. If the hydrogenation rate is too low, the transparency tends to decrease due to coloring, and if the hydrogenation rate is too high, the production cost tends to increase. The hydrogenation rate can be determined from the ratio of the ¹ H-NMR peak intensities of hydrogen in the aromatic ring before hydrogenation and after hydrogenation. As the alicyclic petroleum resin, a cyclohexane ring-containing hydrogenated petroleum resin and a dicyclopentadiene type hydrogenated petroleum resin are particularly preferable. The petroleum resins may be used alone or in combination of two or more. The number average molecular weight Mn of the petroleum resin is preferably 100 to 2,000, more preferably 700 to 1,500, and further preferably 500 to 1,000.

<(D) Curing agent>
The resin composition of the present invention may further contain (D) a curing agent (hereinafter sometimes abbreviated as “(D) component”) from the viewpoint of improving the curing performance of the resin composition. The component (D) is not particularly limited, but examples thereof include amine-based curing agents, guanidine-based curing agents, imidazole-based curing agents, phosphonium-based curing agents, and phenol-based curing agents. The component (D) may be used alone or in combination of two or more.

  The amine-based curing agent is not particularly limited, but quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide; DBU (1,8-diazabicyclo [5.4.0] undecene-7), DBN ( 1,5-diazabicyclo [4.3.0] nonene-5), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, DBU-phenol novolac resin salt, etc. Diazabicyclo compounds; tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol and salts thereof, aromatic dimethylurea, aliphatic dimethylurea, aromatic Dimethylurea compounds such as dimethylurea; and the like. These may be used alone or in combination of two or more.

  The guanidine-based curing agent is not particularly limited, but includes dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4] .0] deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl Biguanide, 1-allyl biguanide, 1-phenyl biguanide, - (o-tolyl) biguanide, and the like. These may be used alone or in combination of two or more.

  The imidazole-based curing agent is not particularly limited, but 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl-imidazole, 2-phenyl-4. , 5-bis (hydroxymethyl) -imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-imidazole, 2-dodecyl-imidazole, 2-heptadecyl imidazole, 1,2-dimethyl-imidazole and the like can be mentioned. These may be used alone or in combination of two or more.

  The phosphonium-based curing agent is not particularly limited, but includes triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) tri Examples thereof include phenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. These may be used alone or in combination of two or more.

  The type of the phenol-based curing agent is not particularly limited, but MEH-7700, MEH-7810, MEH-7851 (manufactured by Meiwa Kasei Co.), NHN, CBN, GPH (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, SN190. , SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei Co., Ltd.), TD2090 (manufactured by DIC), and the like. Specific examples of the triazine skeleton-containing phenolic curing agent include LA3018 (manufactured by DIC). Specific examples of the triazine skeleton-containing phenol novolac curing agent include LA7052, LA7054, LA1356 (manufactured by DIC) and the like. These may be used alone or in combination of two or more.

  The content of component (D) in the resin composition is not particularly limited. However, when the component (D) is used, the content thereof is preferably 5% by mass or less per 100% by mass of the total non-volatile components in the resin composition from the viewpoint of preventing a decrease in moisture permeability resistance. It is more preferably not more than mass%. On the other hand, from the viewpoint of suppressing tack, when the component (D) is used, its content is preferably 0.01% by mass or more, based on 100% by mass of the total non-volatile components in the resin composition, and 0.05. It is more preferably at least mass%.

<(E) Resin having functional group capable of reacting with epoxy group>
When a polyolefin resin having an epoxy group is used as the component (A) in the resin composition of the present invention, a functional group capable of reacting with the epoxy group (E) as a component for forming a crosslinked structure with the component (A). It is desirable to use a resin having a (hereinafter sometimes referred to as “component (E)”). Examples of the functional group capable of reacting with the epoxy group include a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group and an acid anhydride group, and an acid anhydride group is preferable. Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride, and the like. As the resin, a polyolefin resin (however, excluding the polyolefin resin having an acid anhydride group which is the component (A)), an acrylic resin, a melamine resin, a phenol resin, a urea resin, a polyester resin, an alkyd resin, a polyurethane, a polyimide Examples thereof include resins, and polyolefin resins are preferable. The polyolefin resin as the component (E) is the same as the above-mentioned component (A) except that it has a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group or the like as a functional group instead of an acid anhydride group. A polyolefin resin is mentioned, and polybutene is preferable.

  The content of component (E) in the resin composition is not particularly limited. However, when the component (E) is used, the content thereof is preferably 30% by mass or less based on 100% by mass of the total non-volatile content in the resin composition from the viewpoint of preventing the deterioration of the moisture resistance. It is more preferably not more than mass%. On the other hand, in the case of using the component (E) from the viewpoint of suppressing tack, the content thereof is preferably 5% by mass or more, and 10% by mass or more per 100% by mass of the total nonvolatile content in the resin composition. More preferable.

<(F) Resin having functional group capable of reacting with acid anhydride group>
In the resin composition of the present invention, when a polyolefin resin having an acid anhydride group is used as the component (A), it reacts with the acid anhydride group (F) as a component for forming a crosslinked structure with the component (A). It is desirable to use a resin having a functional group capable of controlling (hereinafter sometimes abbreviated as “(F) component”). Examples of the functional group capable of reacting with the acid anhydride group include a hydroxyl group, a primary or secondary amino group, a thiol group, an epoxy group and an oxetane group, and an epoxy group is preferable. Examples of the resin include polyolefin resins (excluding the polyolefin resin having an epoxy group as the component (A)), acrylic resin, melamine resin, phenol resin, urea resin, polyester resin, alkyd resin, polyurethane, polyimide resin, etc. And a polyolefin resin is preferable. The polyolefin resin as the component (F) has the functional group described above, except that it has a hydroxyl group, a primary or secondary amino group, a thiol group, an epoxy group, an oxetane group, etc., instead of an epoxy group ( The same polyolefin-based resin as the component A) can be mentioned, and polybutene is preferable.

  The content of the component (F) in the resin composition is not particularly limited. However, in the case of using the component (F) from the viewpoint of preventing a decrease in moisture permeability, the content thereof is preferably 30% by mass or less per 100% by mass of the total nonvolatile content in the resin composition, It is more preferably not more than mass%. On the other hand, in the case of using the component (F) from the viewpoint of suppressing tack, the content thereof is preferably 5% by mass or more, and 10% by mass or more per 100% by mass of the total nonvolatile content in the resin composition. More preferable.

<(G) Plasticizer>
The resin composition of the present invention may further contain (G) a plasticizer (hereinafter sometimes abbreviated as “(G) component”). By using the component (G), the flexibility and moldability of the resin composition can be improved. The component (G) is not particularly limited, but a liquid material at room temperature is preferably used. Specific examples of the plasticizer include paraffin-based process oil, naphthene-based process oil, liquid paraffin, polyethylene wax, polypropylene wax, mineral oil such as vaseline, castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, olive oil. And other liquid oils such as vegetable oils, liquid polybutene, hydrogenated liquid polybutene, liquid polybutadiene, hydrogenated liquid polybutadiene, and the like. As the plasticizer used in the present invention, liquid polyα-olefins are preferable, and liquid polybutadiene is particularly preferable. Further, as the liquid poly-α-olefin, those having a low molecular weight are preferable from the viewpoint of adhesiveness, and those having a weight average molecular weight of 500 to 5,000, more preferably 1,000 to 3,000 are preferable. These plasticizers may be used alone or in combination of two or more. The term "liquid" as used herein means the state of the plasticizer at room temperature (25 ° C). When the component (G) is used, the content thereof is preferably 50% by mass or less based on 100% by mass of the total nonvolatile content in the resin composition from the viewpoint of not adversely affecting the organic EL device.

<Other additives>
The resin composition of the present invention may optionally contain various additives other than the above-mentioned components to the extent that the effects of the present invention are not impaired. Examples of such additives include resins other than the above-mentioned components (A), (E) and (F) (for example, epoxy resin, urethane resin, acrylic resin, polyamide resin, etc.), silica, barium sulfate. , Talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, zircon Inorganic fillers such as barium acid salt and calcium zirconate (excluding hygroscopic metal oxides); organic fillers such as rubber particles, silicone powder, nylon powder, fluororesin powders; thickeners such as Orben and Benton; Silicon-based, fluorine-based, polymer-based defoamer or level Grayed agent; triazole compounds, thiazole compounds, triazine compounds, adhesion imparting agents such as porphyrin compounds; and the like.

<Pressure sensitive adhesive>
The encapsulating resin composition of the present invention is preferably a pressure sensitive adhesive. The pressure-sensitive adhesive means an adhesive that adheres only by applying pressure at room temperature for a relatively short time, and is well known to those skilled in the art. Further, the encapsulating resin composition of the present invention is more preferably a pressure-sensitive adhesive having tackiness, containing (C) a tackifying resin.

<Method for producing resin composition>
The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding the solvent and the like to the compounding ingredients and mixing them using a kneading roller or a rotary mixer.

<Use of resin composition>
The resin composition of the present invention is used for sealing electronic parts such as semiconductors, solar cells, high-intensity LEDs, LCDs and EL elements, and preferably optical semiconductors such as solar cells and organic EL elements. The resin composition of the present invention is particularly preferably used for sealing an organic EL device. Specifically, the resin composition of the present invention can be used in order to protect the light emitting portion of the organic EL element from the outside by applying it to the upper portion and / or the periphery (side portion) of the light emitting portion of the organic EL element. .

  When the resin composition of the present invention is used for sealing an organic EL device, the transparency of the sealing layer (resin composition layer) formed by the resin composition can be measured by a spectrophotometer. . The higher the transparency, the better in terms of improving the luminous efficiency of the organic EL element. When glass is used as the reference as described in Examples described later, the total light transmittance (parallel light transmittance) at a wavelength of 450 nm of the sealing layer is preferably 90% or more, and 95% or more. It is particularly preferable to have. The value of the total light transmittance at 450 nm described above is a value measured with a sealing layer (resin composition layer) having a thickness of 20 μm, but the thickness of the sealing layer is generally 3 to It is set in the range of 200 μm.

<Sealing sheet>
The present invention also provides a sealing sheet containing the above-described resin composition of the present invention. Specific embodiments include a support and a sealing sheet having a resin composition layer formed from the resin composition of the present invention on the support. The resin composition layer may be formed by a method known to those skilled in the art. For example, a varnish prepared by dissolving the resin composition of the present invention in an organic solvent is prepared, and the varnish is applied and dried on a support. Can be formed. The organic solvent can be dried by blowing hot air or the like. When the resin composition of the present invention contains a curable component such as a polyolefin resin having an epoxy group, the resin composition layer may be further heated to form a cured resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”), cyclohexanone; acetic acid such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Esters; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like; aromatic mixed solvents such as solvent naphtha and the like. it can. Examples of the aromatic mixed solvent include "Swazol" (manufactured by Maruzen Petroleum Co., Ltd.) and "Ipsol" (manufactured by Idemitsu Kosan Co., Ltd.). The organic solvent may be used alone or in combination of two or more.

  The drying condition is not particularly limited, but 50 to 100 ° C. and 1 to 60 minutes are preferable. By setting the temperature to 50 ° C. or higher, the amount of solvent remaining in the resin composition layer can be easily reduced.

  In the encapsulating resin composition of the present invention, both (1) a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group are used as the component (A), and the component (2) (A) is used. Polyolefin resin having epoxy group is used, and component (E) (that is, resin having functional group capable of reacting with curing agent epoxy group) is used, or (3) Acid anhydride group as component (A) By using a polyolefin-based resin having a component (F) (that is, a resin having a functional group capable of reacting with an acid anhydride group), the resin composition is heated and crosslinked before the sealing step. A structure may be formed, or a crosslinked structure may be formed by heating after the sealing step. For example, in the case of encapsulating an element (for example, an organic EL element) using the encapsulating sheet of the present invention, the resin composition layer may be preheated to form a crosslinked structure before the encapsulating step. Then, the resin composition layer may be heated after the sealing step to form a crosslinked structure. From the viewpoint of reducing the thermal deterioration of the element (for example, organic EL element), it is preferable to preheat before the sealing step to form the crosslinked structure.

  When heating the resin composition layer before the sealing step, the heating conditions are not particularly limited, but the temperature is preferably 50 to 200 ° C, more preferably 100 to 180 ° C, and further preferably 120 to 160 ° C. The heating time is preferably 15 to 120 minutes, more preferably 30 to 100 minutes.

  When the resin composition layer is thermally cured after the sealing step, the curing temperature is preferably 50 to 150 ° C., more preferably 60 to 100 ° C., from the viewpoint of preventing thermal deterioration of the device (for example, organic EL device). , 60 to 80 ° C. is more preferable.

  The thickness of the resin composition layer in the encapsulating sheet is preferably from 3 to 200 μm, more preferably from 5 to 100 μm, even more preferably from 5 to 50 μm.

  As will be described later, when the final sealing structure of interest is a structure in which a sealing base material is laminated on the resin composition layer, the water-permeable portion is only the side portion of the resin composition layer. Therefore, by reducing the layer thickness of the resin composition layer, the area of the side portion in contact with the outside air is reduced. Therefore, it is desirable to reduce the layer thickness of the resin composition layer in order to block moisture. However, if the thickness of the resin composition layer is too small, the element may be damaged when the sealing base material is attached, and the workability in attaching the sealing base material tends to decrease. is there. In addition, setting the thickness of the resin composition layer within the above-mentioned preferable range means that the resin composition after transferring the resin composition layer to a sealing target (for example, a substrate on which an element such as an organic EL element is formed) is sealed. It is also effective in maintaining the uniformity of the layer thickness.

  As the support used for the encapsulating sheet, a support having moisture resistance is preferable. Examples of the moisture-proof support include moisture-proof plastic films and metal foils such as copper foil and aluminum foil. Examples of the moisture-proof plastic film include plastic films having a surface deposited with an inorganic substance such as silicon oxide (silica), silicon nitride, SiCN, and amorphous silicon. Here, examples of the plastic film on the surface of which an inorganic substance is vapor-deposited include polyolefin (eg, polyethylene, polypropylene, polyvinyl chloride, etc.), polyester (eg, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”).) , Polyethylene naphthalate, etc.), polycarbonate, polyimide, and other plastic films are preferable, and PET films are particularly preferable. Examples of commercially available moisture-proof plastic film include Tech Barrier HX, AX, LX, L series (manufactured by Mitsubishi Plastics Co., Ltd.) and more moisture-proof effect than the Tech Barrier HX, AX, LX, L series. For example, an enhanced X-BARRIER (manufactured by Mitsubishi Plastics, Inc.) and the like can be mentioned. Further, as the moisture-proof support, a support having a multilayer structure of two or more layers, for example, a support obtained by laminating the above plastic film and the above metal foil with an adhesive can be used. This is inexpensive and advantageous from the viewpoint of handleability. As the support of the resin composition sheet, a support having no moisture-proof property (for example, a single plastic film having no inorganic substance deposited on the surface) can also be used.

  Although the thickness of the support is not particularly limited, it is preferably 10 to 150 μm, more preferably 20 to 100 μm from the viewpoint of handleability of the encapsulating sheet.

  In addition, the encapsulating sheet of the present invention has a protective film on the surface of the resin composition layer in order to prevent adhesion of dust or the like to the surface of the resin composition layer or scratches before actually used for forming the encapsulation structure. It is preferable that the above-mentioned support is used as the protective film. The protective film may be subjected to a matte treatment, a corona treatment, or a release treatment in advance. Specific examples of the release agent include a fluorine-based release agent, a silicon-based release agent, and an alkyd resin-based release agent. The release agent may be a mixture of different types. The thickness of the protective film is not particularly limited, but is preferably 1 to 40 μm, more preferably 10 to 30 μm.

  The encapsulating sheet of the present invention is used by being laminated on an object to be encapsulated. As used herein, the term "laminate" refers to a state in which the encapsulation target is covered with the encapsulating sheet with the support, and the encapsulation target is covered with the resin composition layer transferred from the encapsulating sheet. Including the state. When the encapsulating sheet is a substrate having a non-moisture proof property (for example, a single plastic film having no inorganic substance deposited on the above surface), the encapsulating sheet is laminated on the object to be encapsulated. After that, it is preferable that the support is peeled off (that is, the resin composition layer is transferred), and then a sealing base material is separately laminated on the resin composition layer. In particular, when the substrate on which the organic EL element is formed (hereinafter, also referred to as “organic EL element formation substrate”) is a sealing target, a mode in which such a sealing base material is laminated is preferable. The "sealing base material" in the present invention means that the moisture-proof support used for the sealing sheet is used alone without forming a resin composition layer on the support. Further, a glass plate, a metal plate, a steel plate or the like which is not suitable for use as a support for a sealing sheet and which has no flexibility, but has a high moisture resistance is also included in the “sealing substrate”.

The encapsulating resin composition of the present invention can be easily made into an encapsulating resin composition having excellent moisture permeation resistance by appropriately adopting the preferable conditions described above. It is preferable that the moisture permeation resistance is less than 15 g / m ² · 24 hr, regardless of the thickness of the resin composition layer (sealing layer), when the water vapor permeation amount is measured under the following conditions. More preferably, it is less than 10 g / m ² · 24 hr. The water vapor transmission rate is the water vapor transmission rate per 1 m ² of the resin composition layer (thickness may be arbitrary) according to JIS Z0208, under the conditions of temperature 40 ° C., humidity 90% RH and 24 hours. taking measurement. The thickness of the sealing layer is not particularly limited, and the thickness may be adjusted so that the moisture permeation resistance becomes the above value. The thickness of the sealing layer is generally set in the range of 3 to 200 μm.

  In the present invention, the total light transmittance at 450 nm of the resin composition layer having a thickness of 20 μm is preferably 90% or more. It can be visually recognized that such a resin composition layer is transparent. The resin composition for encapsulation of the present invention can easily form a resin composition layer (encapsulation layer) having excellent total light transmittance by appropriately adopting the preferable conditions described above. The total light transmittance at 450 nm of the resin composition layer having a thickness of 20 μm is preferably 90% or more, and more preferably 95% or more. The total light transmittance at 450 nm of the resin composition layer was determined by laminating the resin composition layer on a glass plate to form a laminate as described in Examples below (see Examples below for lamination conditions. ), Using a glass plate as a reference. The value of the total light transmittance at 450 nm described above is a measured value of the resin composition layer having a thickness of 20 μm, but the thickness of the resin composition layer is generally in the range of 3 to 200 μm. .

<Organic EL device>
The present invention also provides an organic EL device having an organic EL element sealed with the above-mentioned resin composition of the present invention. For example, the organic EL device of the present invention is obtained by laminating the sealing sheet of the present invention on a substrate having an organic EL element. When the encapsulating sheet is protected by a protective film, the encapsulating sheet is peeled off, and then the encapsulating sheet is laminated on the substrate so that the resin composition layer directly contacts the substrate. The laminating method may be a batch method or a continuous method using rolls.

  When the support of the sealing sheet is a moisture-proof support, after the sealing sheet is laminated on the substrate having the organic EL element, the support is not peeled off and the organic EL element is directly sealed. The process is complete. If heat curing is required after the sealing step, heat curing is performed.

  Generally, the sealing material for an organic EL element needs to be dried before the sealing operation to remove the absorbed water, and the operation is complicated, but a support having moisture resistance is used. Since the encapsulating sheet of the present invention using is highly moisture-permeable, it has a low water absorption rate during storage and device manufacturing operations. Further, the damage given to the organic EL element during the sealing work is also remarkably reduced.

When the encapsulating sheet using a support having no moisture proof property is used, after laminating the encapsulating sheet on the substrate having the organic EL element, the support is peeled off and the exposed resin composition layer is provided with a encapsulating group. The step of sealing the organic EL element is completed by pressing the material. Two or more sealing base materials may be used in combination from the viewpoint of increasing the moisture-proof effect. Further, the thickness of the sealing base material is preferably 5 mm or less, more preferably 1 mm or less, and further preferably 100 μm or less from the viewpoint of making the organic EL device itself thin and light. From the viewpoint of preventing water permeation, it is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more. The pressure at the time of pressure-bonding the sealing substrate is preferably about 0.3 to 10 kgf / cm ² , and when pressure-bonding under heating, 25 ° C to 130 ° C is preferable.

  When the substrate having the organic EL element is a transparent substrate on which the organic EL element is formed, if the transparent substrate side is used as the display surface of the display or the light emitting surface of the lighting device, it becomes a support for the sealing sheet. It is not always necessary to use a transparent material, and a metal plate, a metal foil, an opaque plastic film or plate, or the like may be used. Further, when the substrate having the organic EL element is one in which the organic EL element is formed on the substrate made of an opaque or low-transparency material, the sealing substrate side is placed on the display surface of the display or the light emitting surface of the lighting fixture. Therefore, a transparent plastic film, a glass plate, a transparent plastic plate or the like is used as the sealing substrate.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" in the amounts of components and copolymerized units mean "parts by mass" and "mass%", respectively, unless otherwise specified.

The raw materials used in Examples and Comparative Examples are as follows.
(A) Polyolefin resin / T-YP429 (manufactured by Seikou PMC): Maleic anhydride-modified ethylene-methyl methacrylate copolymer (ethylene unit / methyl methacrylate unit = 68% / 32%, acid anhydride group concentration: 0. 46 mmol / g, number average molecular weight: 2,300)
-T-YP431 (made by Seikou PMC): Glycidyl methacrylate modified ethylene-methyl methacrylate copolymer (epoxy group concentration: 0.64 mmol / g, number average molecular weight: 2,400)
-T-YP430 (manufactured by Seikou PMC): Maleic anhydride-modified ethylene-methyl methacrylate copolymer (ethylene unit / methyl methacrylate unit = 68% / 32%, acid anhydride group concentration: 1.18 mmol / g, number average) (Molecular weight: 4,500)
-T-YP432 (manufactured by Seikou PMC): Glycidyl methacrylate modified ethylene-methyl methacrylate copolymer (epoxy group concentration: 1.63 mmol / g, number average molecular weight: 3,100)
T-YP8920 (manufactured by Seikou PMC): Maleic anhydride-modified styrene-isobutylene-styrene copolymer (styrene unit / isobutylene unit = 20% / 80%, acid anhydride group concentration: 0.464 mmol / g, number average) Molecular weight: 35,800)
-T-YP8930 (manufactured by Seikou PMC): Glycidyl methacrylate modified styrene-isobutylene-styrene copolymer (styrene unit / isobutylene unit = 20% / 80%, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 48) , 700)
-T-YP312 (made by Seikou PMC): Maleic anhydride modified propylene-butene copolymer (propylene unit / butene unit = 71% / 29%, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 60,900)
-T-YP313 (made by Seikou PMC): Glycidyl methacrylate modified propylene-butene copolymer (propylene unit / butene unit = 71% / 29%, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 155,000) )
-T-YP341 (manufactured by Seikou PMC): Glycidyl methacrylate modified propylene-butene copolymer (propylene unit / butene unit: 71% / 29%, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 155,000) )
HV-300M (Toho Chemical Industry Co., Ltd.): maleic anhydride-modified liquid polybutene (concentration of acid anhydride group: 0.77 mmol / g, number average molecular weight: 2,100)
HV-1900 (manufactured by JX Energy Co.): polybutene (number average molecular weight: 2,900)

(B) Metal hydroxide / DHT-4C (manufactured by Kyowa Chemical Industry Co., Ltd.): Semi-calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 15 m ² / g)
DHT-4A-2 (manufactured by Kyowa Chemical Industry Co., Ltd.): Semi-calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 10 m ² / g)
DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.): Hydrotalcite (average particle size: 400 nm, BET specific surface area: 10 m ² / g)

(B ') Hygroscopic metal oxide KW2200 (manufactured by Kyowa Chemical Industry Co., Ltd.): calcined hydrotalcite (average particle diameter: 400 nm, BET specific surface area: 129 m ² / g)
N41S: calcined hydrotalcite (manufactured by Toda Kogyo Co., Ltd.) (average particle size: 40 nm, BET specific surface area: 133 m ² / g)
Moistop # 10 (manufactured by Sankyo Flour Mills): calcium oxide (average particle size: 4 μm, BET specific surface area: 5 m ² / g)
FNM-G (manufactured by Tateho Chemical Industry Co., Ltd.): Magnesium oxide (average particle diameter: 400 nm, BET specific surface area: 74 m ² / g)

(C) Tackifying resin Alcon P125 (manufactured by Arakawa Chemical Co., Ltd.): Cyclohexane ring-containing hydrogenated petroleum resin (softening point 125 ° C.)

(D) Hardener / Amine hardener (2,4,6-tris (diaminomethyl) phenol, hereinafter abbreviated as "TAP".)

Organic solvent / Toluene / Swasol # 1000 (Maruzen Oil Co., Ltd.): Aromatic mixed solvent

  The compositions of Examples and Comparative Examples were prepared by the following procedure. The compounding was carried out in the amounts shown in Tables 1 and 2. In addition, the amounts of components other than the organic solvent described in Tables 1 and 2 are values converted into non-volatile components.

<Example 1>
Cyclohexane ring-containing hydrogenated petroleum resin (Alcon P125, 60% Swazol # 1000 solution) 130 parts, maleic anhydride-modified ethylene-methyl methacrylate copolymer (T-YP429, 20% toluene solution) 120 parts, polybutene (HV- 1900) 60 parts and semi-calcined hydrotalcite (DHT-4C) 100 parts were dispersed with a three-roll mill to obtain a mixture. 90 parts of a glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (T-YP431, 20% toluene solution), 0.5 parts of an amine-based curing agent (TAP) and 170 parts of toluene were added to the obtained mixture to obtain a mixture. The mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish of the resin composition. The resulting varnish was applied uniformly on a release-treated surface of a PET film (thickness 38 μm) treated with a silicone-based release agent with a die coater, and heated at 130 ° C. for 60 minutes to give a thickness of A sealing sheet having a resin composition layer of 20 μm was obtained.

<Example 2>
A varnish of the resin composition and a sealing sheet were produced in the same manner as in Example 1 except that the amount of semi-calcined hydrotalcite (DHT-4C) used was changed from 100 parts to 80 parts.

<Example 3>
In the same manner as in Example 1 except that the same amount of semi-calcined hydrotalcite (DHT-4A-2) was used instead of semi-calcined hydrotalcite (DHT-4C), the varnish of the resin composition and A sealing sheet was produced.

<Example 4>
Varnish of resin composition and encapsulating sheet in the same manner as in Example 1 except that the same amount of hydrotalcite (DHT-4A) was used instead of semi-calcined hydrotalcite (DHT-4C). Was produced.

<Example 5>
Instead of the maleic anhydride-modified ethylene-methyl methacrylate copolymer (T-YP429, 20% toluene solution), the same amount of maleic anhydride-modified ethylene-methyl methacrylate copolymer (T-YP430, 20% toluene solution) was used. Instead of using glycidyl methacrylate modified ethylene-methyl methacrylate copolymer (T-YP431, 20% toluene solution), the same amount of glycidyl methacrylate modified ethylene-methyl methacrylate copolymer (T-YP432, 20% toluene) was used. A varnish of the resin composition and a sealing sheet were produced in the same manner as in Example 1 except that the solution) was used.

<Example 6>
Instead of maleic anhydride-modified ethylene-methylmethacrylate copolymer (T-YP429, 20% toluene solution), the same amount of maleic anhydride-modified styrene-isobutylene-styrene copolymer (T-YP8920, 20% toluene solution). In place of the glycidyl methacrylate modified ethylene-methyl methacrylate copolymer (T-YP431, 20% toluene solution), the same amount of glycidyl methacrylate modified styrene-isobutylene-styrene copolymer (T-YP8930, 20) was used. % Toluene solution), a varnish of the resin composition and a sealing sheet were produced in the same manner as in Example 1.

<Example 7>
Instead of the maleic anhydride-modified ethylene-methyl methacrylate copolymer (T-YP429, 20% toluene solution), the same amount of maleic anhydride-modified propylene-polybutene copolymer (T-YP312, 20% toluene solution) was used. And instead of the glycidyl methacrylate modified ethylene-methyl methacrylate copolymer (T-YP431, 20% toluene solution), the same amount of glycidyl methacrylate modified propylene-butene copolymer (T-YP313, 20% toluene solution) A varnish of the resin composition and a sealing sheet were produced in the same manner as in Example 1 except that was used.

<Example 8>
Instead of 120 parts of maleic anhydride-modified ethylene-methyl methacrylate copolymer (T-YP429, 20% toluene solution), 200 parts of glycidyl methacrylate-modified propylene-butene copolymer (T-YP341, 20% toluene solution) was used. And carried out except that 35 parts of maleic anhydride modified liquid polybutene (HV-300M) was used in place of 90 parts of glycidyl methacrylate modified ethylene-methyl methacrylate copolymer (T-YP431, 20% toluene solution). In the same manner as in Example 1, a varnish of resin composition and a sealing sheet were produced.

<Comparative Example 1>
A varnish of resin composition and a sealing sheet were produced in the same manner as in Example 1 except that calcined hydrotalcite (KW2200) was used instead of semi-calcined hydrotalcite (DHT-4C).

<Comparative example 2>
A varnish of resin composition and a sealing sheet were produced in the same manner as in Example 1 except that calcined hydrotalcite (N41S) was used instead of semi-calcined hydrotalcite (DHT-4C).

<Comparative example 3>
A varnish of resin composition and a sheet for encapsulation were produced in the same manner as in Example 1 except that calcium oxide (moistop # 10) was used instead of the semi-calcined hydrotalcite (DHT-4C). .

<Comparative example 4>
A varnish of the resin composition and a sealing sheet were produced in the same manner as in Example 1 except that magnesium oxide (FNM-G) was used instead of the semi-calcined hydrotalcite (DHT-4C).

  The resin composition layers of the encapsulating sheets of Examples and Comparative Examples obtained as described above were evaluated as follows. The results are shown in Tables 1 and 2.

1. Evaluation of moisture permeation resistance (water vapor transmission amount) Water vapor transmission amount per 1 m ^{2 of} the resin composition layer (thickness: 45 μm) peeled from the support (PET film) of the encapsulating sheets prepared in Examples and Comparative Examples. Was measured under the conditions of a temperature of 40 ° C., a humidity of 90% RH and 24 hours by a method according to JIS Z0208, and evaluated according to the following criteria. The results are shown in Table 1.
Good (○): Water vapor transmission rate is less than 10 g / m ² · 24 hr Poor (△): Water vapor transmission rate is 10 g / m ² · 24 hr or more, less than 20 g / m ² · 24 hr Poor (x): Water vapor transmission rate is 20 g / M ² · 24hr or more

2. Evaluation of Total Light Transmittance The encapsulating sheet (thickness of resin composition layer: 20 μm) produced in Examples and Comparative Examples was cut into a length of 50 mm and a width of 20 mm, and the cut encapsulating sheet was a glass plate ( A batch type vacuum laminator (V-160, manufactured by Nichigo Morton Co., Ltd.) is used for a micro slide glass having a length of 76 mm, a width of 26 mm and a thickness of 1.2 mm, and Matsunami Glass Industry Co., Ltd. white slide glass S1112 edge polishing No. 2). Laminated. The lamination conditions were a temperature of 80 ° C., a pressure reduction time of 30 seconds, and a pressure of 0.3 MPa for 30 seconds. Then, the PET film of the encapsulating sheet was peeled off, and the exposed cured resin composition layer was further laminated with the same glass plate as above to prepare a laminate. The light transmittance spectrum of the obtained laminated body, a fiber type spectrophotometer (MCPD-7700, type 311C, manufactured by Otsuka Electronics Co., Ltd.) equipped with a φ80 mm integrating sphere (type name SRS-99-010, reflectance 99%). External light source unit: Halogen lamp MC-2564 (24V, 150W specification)) was used for measurement, and the total light transmittance at a wavelength of 450 nm was calculated and evaluated according to the following criteria. The distance between the integrating sphere and the sample (laminate) was 0 mm, and glass was used as a reference.
Good (○): 95% or more Acceptable (△): 90% or more, less than 95% Poor (x): Less than 90%

  As shown in Tables 1 and 2, Example 1 using a metal hydroxide (DHT-4C, DHT-4A-2 or DHT-4A) selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite. Nos. 8 to 8 have favorable results of transparency (total light transmittance) as compared with Comparative Examples 1 to 4 using a hygroscopic metal oxide (KW2200, N41S, Moistop # 10 or FNM-G).

  The encapsulating resin composition of the present invention can form a highly transparent encapsulating layer (resin composition layer). Therefore, the encapsulating resin composition of the present invention can be suitably used for encapsulating electronic components (particularly organic EL devices).

  This application is based on Japanese Patent Application No. 2015-193115 filed in Japan, the contents of which are incorporated in full herein.

Claims (14)

A sealing resin composition comprising (A) a polyolefin resin and (B) a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite :
(A) A sealing resin composition in which the polyolefin-based resin contains a polyolefin-based resin having an acid anhydride group and / or a polyolefin-based resin having an epoxy group .   The resin composition according to claim 1, wherein the polyolefin resin (A) contains a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group. The resin composition according to claim 2, which has a crosslinked structure formed by the reaction of an acid anhydride group and an epoxy group. The resin composition according to claim 1, which is a pressure-sensitive adhesive. (A) Polyolefin resin, and
(B) Metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite
A resin composition for sealing, which is a pressure-sensitive adhesive containing Further (C) resin composition according to any one of claims 1 to 5 including a tackifying resin. Furthermore (D) resin composition according to any one of claims 1 to 6 including the curing agent. The resin composition according to any one of claims 1 to 7 which is for sealing an organic EL device. The resin composition according to any one of claims 1 to 9 , wherein the resin composition layer having a thickness of 20 µm has a total light transmittance (parallel light transmittance) at a wavelength of 450 nm of 90% or more. Simplex or sheet for sealing which are formed on both surfaces of the resin composition layer comprising a resin composition support as claimed in any one of claims 1-9. (A) The polyolefin-based resin contains a polyolefin-based resin having an acid anhydride group and a polyolefin-based resin having an epoxy group, and the resin composition layer has a crosslinked structure formed by the reaction of the acid anhydride group and the epoxy group. The encapsulating sheet according to claim 10, which has. The encapsulating sheet according to claim 10 or 11 , which is for encapsulating an organic EL element. The organic EL device having an organic EL device sealed with a resin composition according to any one of claims 1-9. Organic EL devices having a sealed organic EL device with a sealing sheet according to any one of claims 10-12.