KR102612145B1 - Resin composition for sealing - Google Patents

Abstract

The present invention provides a sealing resin composition comprising (A) a polyolefin-based resin, and (B) a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite.

Description

Resin composition for sealing

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

Organic EL (Electroluminescence) devices are light-emitting devices that use organic materials as light-emitting materials, and are a material that has recently been in the spotlight as it can produce high-brightness light emission at low voltage. However, organic EL elements are very weak to moisture, and the organic material itself may deteriorate due to moisture, resulting in lower brightness or no longer emitting light, or the interface between the electrode and the organic EL layer may peel off under the influence of moisture, or the metal may oxidize. There was a problem of high resistance.

When using a thermosetting resin composition as a full-side sealing material, advantages include that the material viscosity before curing is low, making lamination work easy, or that the cured product after thermosetting has high moisture permeability resistance. However, on the other hand, there is a problem that the organic EL element deteriorates due to the heating temperature during thermal curing. In addition, in the conventional can sealing structure, light is blocked by a getter layer built into the sealing space for the purpose of dehydration, so there is a defect in the efficiency of light extraction from the sealing surface side, but in a structure that is completely sealed with a resin composition, the sealing One advantage is that light emission from the surface side can be efficiently extracted.

As sealing materials suitable for avoiding the problem of thermal deterioration of electronic components such as organic EL devices, resin compositions containing polyolefins such as polyisobutylene or polyolefin-based copolymers and a tackifier are known. Additionally, in order to improve moisture permeability resistance, it is known to mix a hygroscopic metal oxide in a sealing resin composition (for example, Patent Documents 1 and 2).

International Publication No. 2011/62167 International Publication No. 2013/108731

If a hygroscopic metal oxide is added to a sealing resin composition containing a polyolefin-based resin in order to increase moisture permeability resistance, a problem of reduced transparency arises. Therefore, the purpose of the present invention is to provide a resin composition for sealing that has good moisture permeability resistance and transparency using a polyolefin resin that can avoid the problem of thermal deterioration.

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

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

[2] (A) The resin composition according to [1], wherein the polyolefin resin includes a polyolefin resin having an acid anhydride group and/or a polyolefin resin having an epoxy group.

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

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

[5] (A) The resin composition according to [1], wherein the polyolefin resin includes a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group.

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

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

[8] The above [5] to [, where the molar ratio (epoxy group:acid anhydride group) of the epoxy group of the polyolefin-based resin having an epoxy group and the acid anhydride group of the polyolefin-based resin having an acid anhydride group is 100:10 to 100:200. 7] The resin composition according to any one of the above.

[9] The above [5] to [, where the molar ratio (epoxy group:acid anhydride group) of the epoxy group of the polyolefin-based resin having an epoxy group and the acid anhydride group of the polyolefin-based resin having an acid anhydride group is 100:50 to 100:150. 7] The resin composition according to any one of the above.

[10] The above [5] to [, where the molar ratio (epoxy group:acid anhydride group) of the epoxy group of the polyolefin-based resin having an epoxy group and the acid anhydride group of the polyolefin-based resin having an acid anhydride group is 100:90 to 100:110. 7] The resin composition according to any one of the above.

[11] The resin composition according to any one of [2] to [10] above, wherein the concentration of the acid anhydride group in the polyolefin resin having an acid anhydride group is 0.05 to 10 mmol/g.

[12] The resin composition according to any one of [2] to [10] above, wherein the concentration of the acid anhydride group in the polyolefin-based 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] above, wherein the concentration of the epoxy group in the polyolefin-based resin having an epoxy group is 0.05 to 10 mmol/g.

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

[15] (A) The resin composition according to any one of [1] to [14] above, wherein the polyolefin-based resin has a number average molecular weight of 1,000,000 or less.

[16] (A) The resin composition according to any one of [1] to [14] above, wherein the polyolefin-based resin has a number average molecular weight of 750,000 or less.

[17] (A) The resin composition according to any one of [1] to [14] above, wherein the polyolefin-based resin has a number average molecular weight of 500,000 or less.

[18] (A) The resin composition according to any one of [1] to [14] above, wherein the polyolefin-based resin has a number average molecular weight of 400,000 or less.

[19] (A) The resin composition according to any one of [1] to [14] above, wherein the polyolefin-based resin has a number average molecular weight of 300,000 or less.

[20] (A) The resin composition according to any one of [1] to [14] above, wherein the polyolefin-based resin has a number average molecular weight of 200,000 or less.

[21] (A) The resin composition according to any one of [1] to [14] above, wherein the polyolefin-based resin has a number average molecular weight of 150,000 or less.

[22] (A) The resin composition according to any one of [1] to [21] above, wherein the polyolefin-based resin has a number average molecular weight of 1,000 or more.

[23] (A) The resin composition according to any one of [1] to [21] above, wherein the polyolefin-based resin has a number average molecular weight of 3,000 or more.

[24] (A) The resin composition according to any one of [1] to [21] above, wherein the polyolefin-based resin has a number average molecular weight of 5,000 or more.

[25] (A) The resin composition according to any one of [1] to [21] above, wherein the polyolefin-based resin has a number average molecular weight of 10,000 or more.

[26] (A) The resin composition according to any one of [1] to [21] above, wherein the polyolefin-based resin has a number average molecular weight of 30,000 or more.

[27] (A) The resin composition according to any one of [1] to [21] above, wherein the polyolefin-based resin has a number average molecular weight of 50,000 or more.

[28] (A) The resin composition according to any one of [1] to [27] above, wherein the polyolefin-based resin content is 80% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[29] (A) The resin composition according to any one of [1] to [27] above, wherein the polyolefin-based resin content is 75% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[30] (A) The resin composition according to any one of [1] to [27] above, wherein the polyolefin-based resin content is 70% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[31] (A) The resin composition according to any one of [1] to [27] above, wherein the polyolefin-based resin content is 60% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[32] (A) The resin composition according to any one of [1] to [27] above, wherein the polyolefin-based resin content is 55% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[33] (A) The resin composition according to any one of [1] to [27] above, wherein the polyolefin-based resin content is 50% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[34] (A) The resin composition according to any one of [1] to [33] above, wherein the polyolefin-based resin content is 1% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

[35] (A) The resin composition according to any one of [1] to [33] above, wherein the polyolefin-based resin content is 3% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

[36] (A) The resin composition according to any one of [1] to [33] above, wherein the polyolefin-based resin content is 5% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

[37] (A) The resin composition according to any one of [1] to [33] above, wherein the polyolefin-based resin content is 7% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

[38] (A) The resin composition according to any one of [1] to [33] above, wherein the polyolefin-based resin content is 10% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

[39] (A) The resin composition according to any one of [1] to [33] above, wherein the polyolefin-based resin content is 35% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

[40] (A) The resin composition according to any one of [1] to [33] above, wherein the polyolefin-based resin content is 40% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

[41] (B) The resin composition according to any one of [1] to [40] above, wherein the metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite consists of semi-calcined hydrotalcite.

[42] (B) The resin according to any one of [1] to [41] above, wherein the BET specific surface area of the metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 1 to 200 m ² /g. Composition.

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

[44] (B) The resin composition according to any one of [1] to [43] above, 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.

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

[46] (B) The above [1] to [45], wherein the content of a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 60% by mass or less per 100% by mass of the total non-volatile matter in the resin composition. ] The resin composition according to any one of the above.

[47] (B) The above [1] to [45], wherein the content of a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 55% by mass or less per 100% by mass of the total non-volatile matter in the resin composition. ] The resin composition according to any one of the above.

[48] (B) The above [1] to [45], wherein the content of a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 50% by mass or less per 100% by mass of the total non-volatile matter in the resin composition. ] The resin composition according to any one of the above.

[49] (B) The above [1] to [45], wherein the content of a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 45% by mass or less per 100% by mass of the total non-volatile matter in the resin composition. ] The resin composition according to any one of the above.

[50] (B) The above [1] to [49], wherein the content of a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 10% by mass or more per 100% by mass of the total non-volatile matter in the resin composition. ] The resin composition according to any one of the above.

[51] (B) The above [1] to [49], wherein the content of a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 20% by mass or more per 100% by mass of the total non-volatile matter in the resin composition. ] The resin composition according to any one of the above.

[52] (B) The above [1] to [49], wherein the content of a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 30% by mass or more per 100% by mass of the total non-volatile matter in the resin composition. ] The resin composition according to any one of the above.

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

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

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

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

[57] (C) The resin composition according to any one of [53] to [56] above, wherein the content of the tackifying resin is 80% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[58] (C) The resin composition according to any one of [53] to [56] above, wherein the content of the tackifying resin is 60% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[59] (C) The resin composition according to any one of [53] to [56] above, wherein the content of the tackifying resin is 50% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[60] (C) The resin composition according to any one of [53] to [56] above, wherein the content of the tackifying resin is 40% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[61] (C) The resin composition according to any one of [53] to [60] above, wherein the content of the tackifying resin is 5% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

[62] (C) The resin composition according to any one of [53] to [60] above, wherein the content of the tackifying resin is 10% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

[63] (C) The resin composition according to any one of [53] to [60] above, wherein the content of the tackifying resin is 15% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

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

[65] (D) The resin composition according to [64] above, wherein the content of the curing agent is 5% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[66] (D) The resin composition according to [64] above, wherein the content of the curing agent is 1% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[67] (D) The resin composition according to any one of [64] to [66] above, wherein the content of the curing agent is 0.01% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

[68] (D) The resin composition according to any one of [64] to [66] above, wherein the content of the curing agent is 0.05% by mass or more per 100% by mass of the total non-volatile matter in the resin composition.

[69] The resin composition according to any one of [1] to [68] above, wherein the content of the hygroscopic metal oxide is 1% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[70] The resin composition according to any one of [1] to [68] above, wherein the content of the hygroscopic metal oxide is 0.5% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

[71] The resin composition according to any one of [1] to [70] above, which is a pressure-sensitive adhesive.

[72] The resin composition according to any one of [1] to [71] above, which is used for sealing an organic EL device.

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

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

[75] A sealing sheet, wherein a resin composition layer made of the resin composition according to any one of [1] to [74] above is formed on one or both sides of a support.

[76] (A) The polyolefin resin includes a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group, and the resin composition layer has a crosslinked structure in which the acid anhydride group and the epoxy group reacted. Sheet for sealing described.

[77] The sealing sheet according to [75] or [76] above, which is for sealing 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] above.

[79] An organic EL device having an organic EL element sealed with the sealing sheet according to any one of [75] to [77] above.

According to the present invention, it becomes possible to provide a sealing composition that uses a polyolefin resin capable of avoiding the problem of thermal deterioration and has both excellent moisture permeability resistance and transparency characteristics.

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

A sealing layer (resin composition layer) having good moisture permeability resistance and transparency can be formed from the sealing resin composition of the present invention. This transparency can be judged by the total light transmittance (parallel line transmittance) of the resin composition layer. The total light transmittance (parallel line 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 the 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, known polyolefin-based resins described in Patent Documents 1 and 2 can be cited. Preferred polyolefin-based resins include polyethylene-based resins, polypropylene-based resins, polybutene-based resins, and polyisobutylene-based resins. These polyolefin-based resins may be homopolymers or copolymers such as random copolymers and block copolymers. Examples of copolymers include copolymers of two or more types of olefins and copolymers of olefins with monomers other than olefins, such as non-conjugated dienes and styrene. Examples of preferred copolymers include ethylene-nonconjugated diene copolymer, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene copolymer, propylene-butene copolymer, propylene-butene-nonconjugated diene. Copolymers, styrene-isobutylene copolymers, styrene-isobutylene-styrene copolymers, etc. may be mentioned. As the polyolefin-based resin, for example, the isobutylene-modified resin described in Patent Document 1, the styrene-isobutylene-modified resin described in Patent Document 2, etc. are preferably used.

(A) The polyolefin resin is a polyolefin resin having an acid anhydride group (i.e., a carbonyloxycarbonyl group (-CO-O-CO-)) from the viewpoint of providing excellent physical properties such as adhesiveness, adhesion and wet heat resistance, and/ Alternatively, it is preferable to include a polyolefin-based resin having an epoxy group. Examples of the acid anhydride group include groups derived from succinic anhydride, groups derived from maleic anhydride, and groups derived from glutaric anhydride. The acid anhydride group may have one or two or more types. The polyolefin resin having an acid anhydride group is, for example, an unsaturated compound having an acid anhydride group, and can be obtained by graft modifying the polyolefin resin under radical reaction conditions. Additionally, an unsaturated compound having an acid anhydride group may be radically copolymerized with an olefin or the like. Similarly, the polyolefin-based resin having an epoxy group is an unsaturated compound having an epoxy group such as glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether, and is a polyolefin. It can be obtained by graft modifying the system resin under radical reaction conditions. Additionally, an unsaturated compound having an epoxy group may be radically copolymerized with an olefin or the like. (A) Component can be used one type or two or more types, and a polyolefin-based resin having an acid anhydride group and a polyolefin-based resin having an epoxy group may be used together.

The concentration of acid anhydride groups in the polyolefin-based resin having acid anhydride groups is preferably 0.05 to 10 mmol/g, and more preferably 0.1 to 5 mmol/g. The concentration of the acid anhydride group can be obtained from the value of the acid value, which is 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. In addition, the amount of polyolefin resin having an acid anhydride group in component (A) is preferably 0 to 70% by mass, more preferably 10 to 50% by mass.

Additionally, the concentration of the epoxy group in the polyolefin-based resin having an epoxy group is preferably 0.05 to 10 mmol/g, and more preferably 0.1 to 5 mmol/g. The epoxy group concentration can be calculated from the epoxy equivalent weight obtained based on JIS K 7236-1995. Furthermore, the amount of polyolefin resin having an epoxy group in component (A) is preferably 0 to 70 mass%, more preferably 10 to 50 mass%.

(A) From the viewpoint of providing excellent physical properties such as moisture permeability resistance, the polyolefin resin preferably contains both a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group. This polyolefin resin forms a crosslinked structure by reacting acid anhydride groups and epoxy groups by heating, and can form a sealing layer with excellent moisture permeability resistance, etc. The formation of the cross-linked structure can be performed after sealing, but for example, when the object to be sealed, such as an organic EL device, is sensitive to heat, it is preferable to seal using a sealing film and to form the cross-linked structure when manufacturing the sealing film. The ratio of the polyolefin-based resin having an acid anhydride group and the polyolefin-based resin having an epoxy group is not particularly limited as long as an appropriate cross-linked structure can be formed, but the molar ratio of the epoxy group to the acid anhydride group (epoxy group: acid anhydride group) is preferably 100. :10 to 100:200, more preferably 100:50 to 100:150, especially preferably 100:90 to 100:110.

(A) The number average molecular weight of the polyolefin resin is not particularly limited, but is preferably 1,000,000 or less, and is preferably 750,000 or less from the viewpoint of achieving good varnish applicability of the resin composition and good compatibility with other components in the resin composition. It is preferable, 500,000 or less is more preferable, 400,000 or less is still more preferable, 300,000 or less is even more preferable, 200,000 or less is particularly preferable, and 150,000 or less is most preferable. On the other hand, from the viewpoint of preventing splashing when applying the varnish of the resin composition, expressing the moisture permeability resistance of the formed resin composition layer, and improving the mechanical strength, this number average molecular weight is preferably 1,000 or more, and more than 3,000. It is preferable, 5,000 or more is more preferable, 10,000 or more is more preferable, 30,000 or more is even more preferable, and 50,000 or more is especially preferable. In addition, the number average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by GPC method was determined using LC-9A/RID-6A manufactured by Shimadzu Seisakusho as a measuring device and Shodex K-800P/K-804L/K-804L manufactured by Showa Denko as a column. , it can be measured at a column temperature of 40°C using toluene, etc. as a mobile phase, and calculated 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, amorphous means that the polyolefin-based resin does not have a clear melting point. For example, when the melting point of the polyolefin-based resin is measured by DSC (differential scanning calorimetry), no clear peak is observed. You can.

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

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

Specific examples of polybutene-based resins include "HV-1900" (polybutene, number average molecular weight: 2,900) manufactured by JX Energie Co., Ltd., and "HV-300M" (maleic anhydride modified liquid polybutene ("HV") manufactured by Toho Chemical Co., Ltd. -300” (modified product with number average molecular weight: 1,400), number average molecular weight: 2,100, number of carboxyl groups constituting the acid anhydride group: 3.2 per molecule, acid value: 43.4 mgKOH/g, acid anhydride group concentration: 0.77 mmol. /g) can be mentioned.

Specific examples of the styrene-isobutylene copolymer include "SIBSTAR T102" manufactured by Kaneka Corporation (styrene-isobutylene-styrene block copolymer, number average molecular weight: 100,000, styrene content: 30% by mass), and "T" manufactured by Seiko PMC Corporation. -YP757B" (maleic anhydride modified styrene-isobutylene-styrene block copolymer, acid anhydride group concentration: 0.464 mmol/g, number average molecular weight: 100,000), "T-YP766" (glycidyl meta) manufactured by Seiko PMC. Crylate-modified styrene-isobutylene-styrene block copolymer, epoxy group concentration: 0.638 mmol/g, number average molecular weight: 100,000), “T-YP8920” manufactured by Seiko PMC (maleic anhydride modified styrene-isobutylene-styrene) Copolymer, acid anhydride group concentration: 0.464 mmol/g, number average molecular weight: 35,800), “T-YP8930” manufactured by Seiko PMC (glycidyl methacrylate modified styrene-isobutylene-styrene copolymer, epoxy group concentration: 0.638mmol/g, number average molecular weight: 48,700).

Specific examples of polyethylene-based resins or polypropylene-based resins include “EPT Ethylene-propylene-dicyclopentadiene copolymer) and "Dafma A4085" (ethylene-butene copolymer) manufactured by Mitsui Chemicals.

As a specific example of the propylene-butene-based copolymer, "T-YP341" manufactured by Seiko PMC (glycidyl methacrylate modified propylene-butene random copolymer, amount of butene units per 100% by mass of the total of propylene units and butene units: 29% by mass, epoxy group concentration: 0.638mmol/g, number average molecular weight: 155,000), “T-YP279” manufactured by Seiko PMC (maleic anhydride modified propylene-butene random copolymer, total of propylene units and butene units 100% by mass) Amount of sugar butene unit: 36% by mass, acid anhydride group concentration: 0.464mmol/g, number average molecular weight: 35,000), “T-YP276” manufactured by Seiko PMC (glycidyl methacrylate modified propylene-butene random copolymer) , Amount of butene unit per 100% by mass of total propylene unit and butene unit: 36 mass%, epoxy group concentration: 0.638 mmol/g, number average molecular weight: 57,000), "T-YP312" manufactured by Seiko PMC (modified with maleic anhydride) Propylene-butene random copolymer, amount of butene units per 100% by mass of the total of propylene units and butene units: 29% by mass, acid anhydride group concentration: 0.464mmol/g, number average molecular weight: 60,900), manufactured by Seiko PMC, “T” -YP313" (glycidyl methacrylate modified propylene-butene random copolymer, amount of butene units per 100% by mass of the total of propylene units and butene units: 29% by mass, epoxy group concentration: 0.638mmol/g, number average molecular weight: 155,000), “T-YP429” manufactured by Seiko PMC (maleic anhydride modified ethylene-methyl methacrylate copolymer, amount of methyl methacrylate units per 100% by mass of the total of ethylene units and methyl methacrylate units: 32 mass %, acid anhydride group concentration: 0.46 mmol/g, number average molecular weight: 2,300), “T-YP430” manufactured by Seiko PMC (maleic anhydride modified ethylene-methyl methacrylate copolymer, ethylene unit and methyl methacrylate unit) Amount of methyl methacrylate unit per 100 mass% of the total: 32 mass%, acid anhydride group concentration: 1.18 mmol/g, number average molecular weight: 4,500), "T-YP431" (glycidyl methacryl) manufactured by Seiko PMC. Rate-modified ethylene-methyl methacrylate copolymer, epoxy group concentration: 0.64 mmol/g, number average molecular weight: 2,400), “T-YP432” manufactured by Seiko PMC (glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer) coalescence, epoxy group concentration: 1.63 mmol/g, number average molecular weight: 3,100).

<(B) a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite>

“Hydrotalcite” in the present invention is a concept that includes uncalcinated natural hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ ·4H ₂ O) and synthetic hydrotalcite (hydrotalcite compound). am. That is, “hydrotalcite” in the present invention means “microcalcined hydrotalcite.”

From the viewpoint of hygroscopicity, semi-calcined hydrotalcite is preferable as component (B). That is, it is preferable that the metal hydroxide is made of semi-calcined hydrotalcite. Here, “semi-fired hydrotalcite” refers to a metal in which the amount of interlayer water is reduced or lost, obtained by calcining hydrotalcite (i.e., natural hydrotalcite or synthetic hydrotalcite (hydrotalcite-type compound)). It refers to hydroxide. When explained using the composition formula, “interlayer water” refers to “H ₂ O” described in the composition formula of the above-described natural hydrotalcite and the synthetic hydrotalcite (hydrotalcite type compound) described later.

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

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

For thermogravimetric analysis, 5 mg of hydrotalcite was weighed in an AL sample pan using TG/DTA EXSTAR6300 manufactured by Hitachi High-Tech Science, and the lid was left open at 30°C under an atmosphere with a nitrogen flow rate of 200 mL/min. It can be carried out from to 550°C under the condition of a temperature increase rate of 10°C/min. The heat weight loss rate is calculated using the following formula:

Thermal weight reduction rate (mass%)

=100×(mass before heating-mass when reaching predetermined temperature)/mass before heating

It can be obtained with

Additionally, hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by peaks and relative intensity ratios measured by powder X-ray diffraction. Semi-calcined hydrotalcite shows, by powder 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 diffraction intensity of the peak or shoulder appearing on the high-angle side (=high-angle side diffraction intensity) is 0.001 to 1,000. On the other hand, hydrotalcite has only one peak around 8 to 18 degrees, 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 outside the above range. Calcined hydrotalcite does not have a characteristic peak in the region of 8° to 18°, but has a characteristic peak in the region of 43°. Powder X-ray diffraction measurement was performed using a powder , the measurement can be performed under the conditions of diffraction angle range (2θ): 5.0131 to 79.9711°. The peak search uses the peak search function of the software attached to the diffraction device, and uses the following parameters: "minimum significance: 0.50, minimum peak chip: 0.01°, maximum peak chip: 1.00°, peak base width: 2.00°, method: second order differentiation. This can be done under the condition of “minimum value.”

For example, in the powder In addition, semi-calcined hydrotalcite "DHT-4C" manufactured by Kyowa Chemical Co., Ltd. has a main peak at 13.2° and a second peak at 11.4°.

Additionally, hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by saturation water absorption. The saturated water absorption of semi-calcined hydrotalcite is 1% by weight or more and less than 20% by weight. Meanwhile, the saturated water absorption of hydrotalcite is less than 1% by weight, and the saturated water absorption of calcined hydrotalcite is 20% by weight or more.

In the present invention, “saturated water absorption rate” means measuring the initial mass by weighing 1.5 g of hydrotalcite, semi-calcined hydrotalcite, or calcined hydrotalcite on a balance, and then measuring the initial mass at 60°C under atmospheric pressure and 90% RH (relative humidity). This refers to the mass increase rate relative to the initial mass when left in a small environmental tester (SH-222 manufactured by Espec) set to 200 hours, and is expressed in the following equation:

Saturated water absorption (mass%)

=100×(mass after moisture absorption-initial mass)/initial mass

It can be obtained with

As synthetic hydrotalcite (hydrotalcite type compound), for example, 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 -} , Cl ^- , NO ₃ ^-, etc., which represent n-valent anions such as 0<x<1, 0≤m<1, and n is a positive number). In formula ( ^{I )} , M ²⁺ is preferably Mg ²⁺ , M ³⁺ is preferably ^{Al 3+} , and A ^n- is preferably ^CO ₃ ^2- .

In addition, as synthetic hydrotalcite (hydrotalcite type compound), for example, 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+ or} Zn ²⁺ , A ^n- represents an n ^- valent anion such as CO ₃ ^{2 -} , Cl ^- , NO ₃ ^- , and x is 2 is a positive number of 2 or less, z is a positive number of 2 or less, m is a positive number, and n is a positive number). In formula (II), M ²⁺ is preferably Mg ²⁺ and A ^n- is preferably CO ₃ ^2- .

The BET specific surface area of component (B) is preferably 1 to 200 m ² /g, and more preferably 5 to 150 m ² /g. (B) The BET specific surface area of the component is determined by adsorbing nitrogen gas to the surface of the sample using a specific surface area measuring device (Macsorb HM Model-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multi-point method. You can get it by doing.

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

(B) Component may be surface-treated with a surface treatment agent. As surface treatment agents used for surface treatment, for example, higher fatty acids, alkyl silanes, silane coupling agents, etc. can be used, and among these, higher fatty acids and alkyl silanes are suitable. One or two or more types of surface treatment agents can be used.

Examples of higher fatty acids include higher fatty acids with 18 or more carbon atoms, such as stearic acid, montanic acid, myristic acid, and palmitic acid, and among these, stearic acid is preferable. These may be used one type or in combination of two or more types. Examples of alkyl silanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, and octyltriene. Toxysilane, n-octadecyldimethyl(3-(trimethoxysilyl)propyl)ammonium chloride, etc. are mentioned. These may be used one type or in combination of two or more types. Silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, and 2-( Epoxy-based silane coupling agents such as 3,4-epoxycyclohexyl)ethyltrimethoxysilane; 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-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, Amino silane coupling agents such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane; ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyl-based silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane; Styryl-based silane coupling agents such as p-styryltrimethoxysilane; Acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; Isocyanate-based silane coupling agents such as 3-isocyanate propyltrimethoxysilane, sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)disulfide and bis(triethoxysilylpropyl)tetrasulfide; Phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole silane, triazine silane, etc. are mentioned. These may be used one type or in combination of two or more types.

Surface treatment of component (B) can be performed, for example, by stirring and dispersing the untreated component (B) at room temperature with a mixer, adding and spraying a surface treatment agent, and stirring for 5 to 60 minutes. As the mixer, a known mixer can be used, and examples include blenders such as V blenders, ribbon blenders, and bubble cone blenders, mixers such as Henschel mixers and concrete mixers, ball mills, and cutter mills. Additionally, when pulverizing the moisture absorbent using a ball mill or the like, it is also possible to mix the above-mentioned higher fatty acids, alkyl silanes, or silane coupling agents to treat the surface. The treatment amount of the surface treatment agent varies depending on the type of component (B) or the type of the surface treatment agent, but is preferably 1 to 10 parts by mass per 100 parts by mass of component (B).

The content of 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 above content is preferably 60% by mass or less, and 55% by mass, per 100% by mass of the total non-volatile matter in the resin composition. % or less is preferable, 50 mass % or less is more preferable, and 45 mass % or less is still more preferable. Furthermore, 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 even more preferably 30% by mass or more, per 100% by mass of the total non-volatile matter in the resin composition. desirable.

Specific examples of component (B) in the present invention include the following:

・DHT-4C (manufactured by Kyowa Chemical 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 Co., Ltd.): semi-calcined hydrotalcite (average particle diameter: 400 nm, BET specific surface area: 10 m ² /g)

・DHT-4A (manufactured by Kyowa Chemical Co., Ltd.): hydrotalcite (average particle diameter: 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, it is preferable that the resin composition of the present invention substantially contains no hygroscopic metal oxide. The content of the hygroscopic metal oxide is preferably in a range such that the transmittance value of the resin composition layer described later is preferably 90% or more, and 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., 0 to 0.5% by mass) per 100% by mass of the total nonvolatile content in the resin composition. %) is more preferable. Examples of hygroscopic metal oxides include calcium oxide, magnesium oxide, strontium oxide, aluminum oxide, barium oxide, calcined dolomite (a mixture containing calcium oxide and magnesium oxide), and calcined hydrotalcite.

<(C) Tackifying resin>

The resin composition of the present invention may further contain (C) tackifying resin (hereinafter sometimes abbreviated as “(C) component”). Tackifying resin, also called tackifier, is a resin that is mixed with a plastic polymer to provide adhesion. (C) The component is not particularly limited and includes terpene resin, modified terpene resin (hydrogenated terpene resin, terpene phenol copolymer resin, aromatic modified terpene resin, etc.), coumarone resin, indene resin, petroleum resin (aliphatic petroleum resin, Hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene petroleum resins and hydrides thereof, etc.) are preferably used.

(C) Examples of commercial products that can be used as the component include the following. Examples of terpene resins include YS Resin PX and YS Resin PXN (all manufactured by Yasuhara Chemical), and examples of aromatic modified terpene resins include YS Resin TO and TR series (all manufactured by Yasuhara Chemical). , Hydrogenated terpene resins include Clearon P, Clearon M, and Clearon K series (all manufactured by Yasuhara Chemical Co., Ltd.), and examples of terpene phenol copolymer resins include YS Polystar 2000, Polystar U, and Polystar. T, Polystar S, MightS G (all manufactured by Yasuhara Chemical Co., Ltd.), etc., and as hydrogenated alicyclic petroleum resins, Escorez 5300 series, 5600 series (all manufactured by Exxon Mobil Co., Ltd.), etc. Examples of aromatic petroleum resins include ENDEX 155 (manufactured by Eastman Co., Ltd.), examples of aliphatic aromatic copolymerized petroleum resins include QuintoneD 100 (manufactured by Nippon Zeon Co., Ltd.), and examples of alicyclic petroleum resins include Quintone 1325 and Quintone 1345 ( Examples of cyclohexane ring-containing hydrogenated petroleum resins include Alcon P100, Alcon P125, and Alcon P140 (all manufactured by Arakawa Chemical Company), and examples of cyclohexane ring-containing saturated hydrocarbon resins include Alcon P100, Alcon P125, and Alcon P140 (all manufactured by Arakawa Chemical Company). TFS13-030 (manufactured by Arakawa Chemical Company) etc. can be mentioned.

The softening point of component (C) is preferably 50 to 200°C, more preferably 90 to 180°C, and 100 to 150°C from the viewpoint of softening the sheet in the lamination process of the resin composition sheet and having the desired heat resistance. It is more desirable. In addition, the softening point is measured by the ring and ball method according to JIS K2207.

(C) Component may be used one type or in combination of two or more types. The content of component (C) in the resin composition is not particularly limited. However, from the viewpoint of maintaining good moisture permeability resistance of the resin composition, when component (C) is used, its content is preferably 80% by mass or less, and 60% by mass or less, per 100% by mass of the total non-volatile matter in the resin composition. It is more preferable, 50 mass% or less is further preferable, and 40 mass% or less is especially preferable. On the other hand, from the viewpoint of having sufficient adhesiveness, when using component (C), its content is preferably 5% by mass or more, and more preferably 10% by mass or more, per 100% by mass of the total non-volatile matter in the resin composition. , 15% by mass or more is more preferable.

Among these, petroleum resin is preferable from the viewpoint of adhesiveness, moisture permeability resistance, transparency, etc. of the resin composition. Examples of the petroleum resin include aliphatic petroleum resin, aromatic petroleum resin, aliphatic aromatic copolymerized petroleum resin, and alicyclic petroleum resin. Among these, from the viewpoint of adhesiveness, moisture permeability resistance, compatibility, etc. of the resin composition, aromatic petroleum resins, aliphatic aromatic copolymerized petroleum resins, and alicyclic petroleum resins are more preferable. Also, from the viewpoint of improving transparency, alicyclic petroleum resins are particularly preferable. The alicyclic petroleum resin may be obtained by hydrogenating an aromatic petroleum resin. In this case, the hydrogenation rate of the alicyclic petroleum resin is preferably 30 to 99%, more preferably 40 to 97%, and even more preferably 50 to 90%. If the hydrogenation rate is too low, the problem of transparency decreasing due to coloring tends to occur, and if the hydrogenation rate is too high, production costs tend to increase. The hydrogenation rate can be determined by the ratio of the peak intensity of ¹ H-NMR of the hydrogen of the aromatic ring before and after hydrogenation. As the alicyclic petroleum resin, cyclohexane ring-containing hydrogenated petroleum resin and dicyclopentadiene-based hydrogenated petroleum resin are particularly preferable. Petroleum resins may be used singly or in combination of two or more types. The number average molecular weight (Mn) of the petroleum resin is preferably 100 to 2,000, more preferably 700 to 1,500, and still more preferably 500 to 1,000.

<(D) Hardener>

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

There are no particular restrictions on the amine-based curing agent, and include 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 -diazabicyclo compounds such as p-toluenesulfonate, DBU-formate, and DBU-phenol novolak resin salt; Tertiary amines such as benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(diaminomethyl)phenol, and their salts; dimethyl such as aromatic dimethyl urea, aliphatic dimethyl urea, and aromatic dimethyl urea Urea compounds, etc. can be mentioned. These may be used one type or in combination of two or more types.

There are no particular restrictions on the guanidine-based curing agent, but include 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]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca -5-N, 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, 1-(o-tolyl) biguanide, etc. These may be used one type or in combination of two or more types.

There are no particular restrictions on the imidazole-based curing agent, but include 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-heptadecylimidazole, 1,2-dimethyl-imidazole, etc. These may be used one type or in combination of two or more types.

There are no particular restrictions on the phosphonium-based curing agent, but include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, and (4-methylphenyl)tri. Phenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc. are mentioned. These may be used one type or in combination of two or more types.

There are no particular restrictions on the type of phenol-based hardener, but include MEH-7700, MEH-7810, MEH-7851 (manufactured by Meiwakasei Co., Ltd.), NHN, CBN, GPH (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, Examples include SN485, SN495, SN375, SN395 (manufactured by Doto Kasei Corporation), and TD2090 (manufactured by DIC Corporation). Specific examples of the phenol-based curing agent containing the triazine skeleton include LA3018 (manufactured by DIC). Specific examples of the triazine skeleton-containing phenol novolak curing agent include LA7052, LA7054, and LA1356 (manufactured by DIC). These may be used one type or in combination of two or more types.

The content of component (D) in the resin composition is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeability resistance, when using component (D), its content is preferably 5% by mass or less, and more preferably 1% by mass or less, per 100% by mass of the total non-volatile matter in the resin composition. do. On the other hand, from the viewpoint of suppressing tack, when using component (D), its content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, per 100% by mass of the total non-volatile matter in the resin composition.

<(E) Resin having a functional group that can react with an epoxy group>

In the resin composition of the present invention, when using a polyolefin-based resin having an epoxy group as component (A), as a component for forming a crosslinked structure with component (A), (E) a resin having a functional group capable of reacting with an epoxy group It is preferable to use (hereinafter sometimes abbreviated as “(E) component”). Functional groups capable of reacting with the epoxy group include hydroxyl groups, phenolic hydroxyl groups, amino groups, carboxyl groups, and acid anhydride groups, with acid anhydride groups being preferred. Examples of the acid anhydride group include groups derived from succinic anhydride, groups derived from maleic anhydride, and groups derived from glutaric anhydride. Resins include polyolefin resins (excluding polyolefin resins having an acid anhydride group as component (A)), acrylic resins, melamine resins, phenol resins, urea resins, polyester resins, alkyd resins, polyurethane, and polyimide resins. etc. are mentioned, and polyolefin-based resin is preferable. Examples of the polyolefin-based resin that is component (E) include polyolefin-based resins similar to the component (A) described above, except that the functional group is not an acid anhydride group but has a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxyl group, etc. Butene is preferred.

The content of component (E) in the resin composition is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeability resistance, when using component (E), its content is preferably 30% by mass or less, and more preferably 20% by mass or less, per 100% by mass of the total non-volatile matter in the resin composition. do. On the other hand, from the viewpoint of suppressing tack, when using component (E), its content is preferably 5% by mass or more, and more preferably 10% by mass or more, per 100% by mass of the total non-volatile matter in the resin composition.

<(F) Resin having a functional group capable of reacting with an acid anhydride group>

In the resin composition of the present invention, when using a polyolefin-based resin having an acid anhydride group as component (A), as a component for forming a crosslinked structure with component (A), (F) a functional group capable of reacting with an acid anhydride group is added. It is preferable to use a resin (hereinafter sometimes abbreviated as “(F) component”) having. Functional groups capable of reacting with acid anhydride groups include hydroxyl groups, primary or secondary amino groups, thiol groups, epoxy groups, oxetane groups, etc., with epoxy groups being preferred. Resins include polyolefin resins (excluding polyolefin resins having an epoxy group as component (A)), acrylic resins, melamine resins, phenol resins, urea resins, polyester resins, alkyd resins, polyurethane, polyimide resins, etc. can be mentioned, and polyolefin-based resin is preferable. The polyolefin resin that is the component (F) is the same polyolefin resin as the component (A) 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 as a functional group. Resins include, and polybutene is preferred.

The content of component (F) in the resin composition is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeability resistance, when using component (F), its content is preferably 30% by mass or less, and more preferably 20% by mass or less, per 100% by mass of the total non-volatile matter in the resin composition. do. On the other hand, from the viewpoint of suppressing tack, when using component (F), its content is preferably 5% by mass or more, and more preferably 10% by mass or more, per 100% by mass of the total non-volatile matter in the resin composition.

<(G) Plasticizer>

The resin composition of the present invention may further contain (G) a plasticizer (hereinafter sometimes abbreviated as “(G) component”). By using component (G), the flexibility and moldability of the resin composition can be improved. (G) The component is not particularly limited, but materials that are liquid at room temperature can be suitably used. Specific examples of plasticizers include paraffinic process oil, naphthenic process oil, liquid paraffin, polyethylene wax, polypropylene wax, mineral oil such as vaseline, vegetable oil such as castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, palm oil, and olive oil, and liquid poly. Liquid poly alpha olefins such as butene, hydrogenated liquid polybutene, liquid polybutadiene, and hydrogenated liquid polybutadiene can be mentioned. As the plasticizer used in the present invention, liquid poly alpha olefins are preferable, and liquid polybutadiene is especially preferable. In addition, the liquid poly-α-olefin preferably has a low molecular weight from the viewpoint of adhesiveness, and preferably has a weight average molecular weight in the range of 500 to 5,000, and further preferably 1,000 to 3,000. These plasticizers may be used individually or in combination of two or more types. In addition, “liquid phase” here refers to the state of the plasticizer at room temperature (25°C). When using component (G), from the viewpoint of not adversely affecting the organic EL element, its content is preferably 50% by mass or less per 100% by mass of the total non-volatile matter in the resin composition.

<Other additives>

The resin composition of the present invention may optionally contain various additives other than the above-mentioned components to the extent that they do not impair the effects of the present invention. Examples of such additives include, for example, resins other than the components (A), (E), and (F) (e.g., epoxy resins, urethane resins, acrylic resins, polyamide resins, etc.), silica, and sulfuric acid. Barium, 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, barium zirconate, calcium zirconate, etc. inorganic fillers (excluding hygroscopic metal oxides); Organic fillers such as rubber particles, silicone powder, nylon powder, and fluororesin powder; Thickeners such as orben and bentone; Silicone-based, fluorine-based, and polymer-based defoamer or leveling agent; Adhesion imparting agents such as triazole compounds, thiazole compounds, triazine compounds, and porphyrin compounds can be mentioned.

<Pressure sensitive adhesive>

It is preferable that the resin composition for sealing of the present invention is a pressure-sensitive adhesive. Pressure-sensitive adhesive refers to an adhesive that bonds only by applying pressure at room temperature for a relatively short period of time, and is well known to those skilled in the art. Moreover, it is more preferable that the sealing resin composition of the present invention contains (C) a tackifying resin and is a pressure-sensitive adhesive having tackiness.

<Method for producing resin composition>

The method for producing the resin composition of the present invention is not particularly limited, and examples include a method of adding a solvent, etc. to the blended components as needed and mixing them using a kneading roller, a rotary mixer, etc.

<Use of resin composition>

The resin composition of the present invention is used for sealing electronic components such as semiconductors, solar cells, high-brightness LEDs, LCDs, and EL devices, and preferably optical semiconductors such as solar cells and organic EL devices. The resin composition of the present invention is particularly suitably used for sealing organic EL devices. Specifically, the resin composition of the present invention can be used to protect the light-emitting part of the organic EL element from the outside by applying it to the top and/or around (side) the light-emitting part 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 that it improves the luminous efficiency of the organic EL device. When glass is used as a reference as described in the examples described later, the total light transmittance (parallel line transmittance) at a wavelength of 450 nm of the sealing layer is preferably 90% or more, and particularly preferably 95% or more. In addition, the value of the total light transmittance at 450 nm described above is a measurement value for a sealing layer (resin composition layer) with a thickness of 20 μm, but the thickness of the sealing layer is generally set in the range of 3 to 200 μm.

<Sealing sheet>

The present invention also provides a sealing sheet containing the resin composition of the present invention described above. A specific embodiment includes a sealing sheet having a support and a resin composition layer formed on the support from the resin composition of the present invention. The resin composition layer may be formed by a method known to those skilled in the art. For example, it can be formed by preparing a varnish in which the resin composition of the present invention is dissolved in an organic solvent, and applying and drying the varnish on a support. Drying of the organic solvent can be carried out by hot air spraying or the like. Additionally, 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 additionally 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”), and cyclohexanone; Acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; Carbitols such as cellosolve and butylcarbitol; Aromatic hydrocarbons such as toluene and xylene; Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.; Aromatic mixed solvents such as solvent naphtha can be mentioned. Examples of aromatic mixed solvents include "Suwasol" (manufactured by Maruzenseki Yu Co., Ltd., brand name) and "Ipsol" (manufactured by Idemitsu Kosan Co., Ltd., brand name). Organic solvents may be used singly or in combination of two or more types.

Drying conditions are not particularly limited, but are preferably 1 to 60 minutes at 50 to 100°C. By setting it to 50°C or higher, it becomes easy to reduce the amount of solvent remaining in the resin composition layer.

In the sealing resin composition of the present invention, (1) both a polyolefin-based resin having an acid anhydride group and a polyolefin-based resin having an epoxy group are used as the (A) component, or (2) a polyolefin-based resin having an epoxy group is used as the (A) component. A resin is used, and component (E) (i.e., a resin having a functional group capable of reacting with the curing agent epoxy group) is used, or (3) a polyolefin-based resin having an acid anhydride group is used as the component (A), and By using component (F) (i.e., a resin having a functional group capable of reacting with an acid anhydride group), the resin composition may be heated before the sealing process to form a cross-linked structure, or it may be heated after the sealing process to form a cross-linked structure. It's also good. For example, when sealing an element (for example, an organic EL element) using the sealing sheet of the present invention, the resin composition layer may be heated in advance to form a crosslinked structure before the sealing process. Later, the resin composition layer may be heated to form a crosslinked structure. From the viewpoint of reducing thermal deterioration of the device (e.g., organic EL device), it is preferable to form a crosslinked structure by heating in advance before the sealing process.

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

When thermally curing the resin composition layer after the sealing process, the curing temperature is preferably 50 to 150°C, and more preferably 60 to 100°C, from the viewpoint of preventing thermal deterioration of the device (e.g., organic EL device). And, 60 to 80°C is more preferable.

The thickness of the resin composition layer in the sealing sheet is preferably 3 to 200 μm, more preferably 5 to 100 μm, and still more preferably 5 to 50 μm.

In addition, as will be described later, when the desired final sealing structure is a structure in which a sealing base material is laminated on a resin composition layer, the portion through which moisture can infiltrate is only the side portion of the resin composition layer. By thinning the layer thickness, the area in contact with the outside air on the side becomes smaller. Therefore, it is preferable to reduce the thickness of the resin composition layer to block moisture. However, if the thickness of the resin composition layer is too small, there is a risk of damaging the element when bonding the sealing substrate, and workability when bonding the sealing substrate tends to decrease. In addition, setting the thickness of the resin composition layer within the above appropriate range maintains uniformity of the thickness of the resin composition layer after transferring the resin composition layer to the sealing target (for example, a substrate on which elements such as organic EL elements are formed). It is also valid for

As a support used for a sealing sheet, a support having moisture resistance is preferable. Examples of the support having moisture resistance include plastic films having moisture resistance and metal foils such as copper foil and aluminum foil. Examples of moisture-proof plastic films include plastic films in which inorganic substances such as silicon oxide (silica), silicon nitride, SiCN, and amorphous silicon are deposited on the surface. Here, plastic films on which inorganic substances are deposited on the surface include, for example, polyolefin (e.g., polyethylene, polypropylene, polyvinyl chloride, etc.), polyester (e.g., polyethylene terephthalate (hereinafter referred to as “PET”) Plastic films such as (sometimes abbreviated), polyethylene naphthalate, etc.), polycarbonate, and polyimide are suitable, and PET film is especially preferable. Examples of commercially available moisture-proof plastic films include Tech Barrier HX, AX, LX, L series (manufactured by Mitsubishi Jushi Corporation) and (manufactured by Mitsubishi Jushi Corporation) etc. can be mentioned. Additionally, as a support having moisture resistance, a support having a multi-layer structure of two or more layers, for example, a support made by attaching the above-mentioned plastic film and the above-described metal foil via an adhesive, can be used. This is inexpensive and is also advantageous from the viewpoint of handling. Additionally, a non-moisture-proof support (for example, a single piece of plastic film with no inorganic substance deposited on the surface) can be used as the support for the resin composition sheet.

The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, and more preferably 20 to 100 μm from the viewpoint of handling of the sealing sheet, etc.

In addition, until the sealing sheet of the present invention is actually used to form a sealing structure, the surface of the resin composition layer is preferably protected with a protective film in order to prevent adhesion of dust, etc. to the surface of the resin composition layer or scratches. , As a protective film, the plastic film exemplified as the above-mentioned support can be used. The protective film may be subjected to a release treatment in addition to mat treatment and corona treatment in advance. Specific examples of the mold release agent include fluorine-based mold release agents, silicone-based mold release agents, and alkyd resin-based mold release agents. Different types of mold release agents may be mixed and used. The thickness of the protective film is also not particularly limited, but is preferably 1 to 40 μm, and more preferably 10 to 30 μm.

The sealing sheet of the present invention is used by laminating it to a sealing object. “Laminate” as used herein includes a state in which the object to be sealed is covered with a sealing sheet provided with a support, as well as a state in which the object to be sealed is covered with a resin composition layer transferred from the sealing sheet. When using a sealing sheet in which the support is a support that does not have moisture resistance (for example, a simple plastic film with no inorganic material deposited on the surface described above), the sealing sheet is laminated to the object to be sealed, and then the support is peeled off. (That is, the resin composition layer is transferred), and then it is preferable to separately laminate the sealing substrate 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 the object to be sealed, an arrangement in which such a sealing substrate is laminated is preferred. In addition, the "sealing base material" referred to in the present invention refers to the moisture-proof support used in the sealing sheet being used alone without forming a resin composition layer thereon. In addition, plates that do not have flexibility but have high moisture resistance, such as glass plates, metal plates, and steel plates, that are not suitable for use as a support for a sealing sheet are also included in the “sealing base material.”

The sealing resin composition of the present invention can be easily converted into a sealing resin composition excellent in moisture permeability resistance by appropriately adopting the preferred conditions described above. The moisture permeability resistance does not depend on the thickness of the resin composition layer (sealing layer), and when the water vapor permeation amount is measured under the following conditions, the water vapor permeation amount is preferably less than 15 g/m ² ·24 hr, and less than 10 g/m ² ·24 hr. It is more desirable. The water vapor permeation amount per 1 m ² of the resin composition layer (the thickness may be arbitrary) is measured by a method based on JIS Z0208 under the conditions of a temperature of 40°C, humidity of 90% RH, and 24 hours. The thickness of the sealing layer is not particularly limited, and the thickness may be adjusted so that the moisture permeability resistance is preferably the above value. The thickness of the sealing layer is generally set in the range of 3 to 200 μm.

In the present invention, it is preferable that the total light transmittance at 450 nm of the resin composition layer having a thickness of 20 μm is 90% or more. This resin composition layer can be recognized as transparent when viewed with the eye. The resin composition for sealing of the present invention can easily form a resin composition layer (sealing layer) with excellent total light transmittance by appropriately employing the preferred 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 is described in the examples described later, and the resin composition layer is laminated on a glass plate to form a laminate (refer to the examples disclosed later for lamination conditions), and the glass plate is used as a reference. It is calculated. In addition, the value of the total light transmittance at 450 nm described above is a measurement value of a 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 resin composition of the present invention described above. For example, the organic EL device of the present invention can be obtained by laminating the sealing sheet of the present invention to a substrate having an organic EL element. When the sealing sheet is protected with a protective film, it is peeled off, and then the sealing sheet is laminated on the substrate so that the resin composition layer is in direct contact with the substrate. The laminate method may be a batch method or a continuous method using rolls.

When the support of the sealing sheet is a support having moisture resistance, after the sealing sheet is laminated on a substrate having an organic EL element, the sealing process of the organic EL element is completed as is without peeling off the support. If thermal curing is necessary after the sealing process, thermal curing is performed.

In general, materials for sealing organic EL elements need to be dried before sealing to remove added moisture, and the process is complicated. However, the sealing sheet of the present invention using a moisture-proof support has high moisture permeability resistance. Therefore, the absorption rate during storage or device manufacturing work is also low. Additionally, damage to the organic EL element during sealing work is also significantly reduced.

When using a sealing sheet using a support that does not have moisture resistance, the sealing sheet is laminated to a substrate having an organic EL element, then the support is peeled off, and the sealing base is pressed to the exposed resin composition layer, thereby sealing the organic EL element. This is done. From the viewpoint of high moisture prevention effect, two or more sealing materials may be used by joining them together. Additionally, from the viewpoint of making the organic EL device itself thin and light, the thickness of the sealing substrate is preferably 5 mm or less, more preferably 1 mm or less, and still more preferably 100 μm or less. Additionally, from the viewpoint of preventing moisture penetration, 5 μm or more is preferable, 10 μm or more is more preferable, and 20 μm or more is still more preferable. The appropriate pressure when compressing the sealing substrate is about 0.3 to 10 kgf/cm ² , and when compressing under heating, 25°C to 130°C is appropriate.

When the substrate having the organic EL element is one in which the organic EL element is formed on a transparent substrate, and the side of the transparent substrate is used as the display surface of a display or the light emitting surface of a lighting fixture, it is not necessary to use a transparent material for the support of the sealing sheet. , metal plate, metal foil, opaque plastic film or plate, etc. may be used. In addition, when the substrate having the organic EL element is one in which the organic EL element is formed on a substrate made of an opaque or low-transparency material, it is necessary to use the sealing substrate side as the display surface of a display or the light emitting surface of a lighting fixture, so that the sealing substrate side Transparent plastic films, glass plates, transparent plastic plates, etc. are used.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, in the following description, “part” and “%” in the amounts of components and copolymerization units mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

The raw materials used in the examples and comparative examples are as follows.

(A) Polyolefin resin

T-YP429 (manufactured by Seiko PMC): maleic anhydride modified ethylene-methyl methacrylate copolymer (ethylene unit/methyl methacrylate unit = 68%/32%, acid anhydride group concentration: 0.46 mmol/g, water Average molecular weight: 2,300)

T-YP431 (manufactured by Seiko 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 Seiko PMC): maleic anhydride modified ethylene-methyl methacrylate copolymer (ethylene unit/methyl methacrylate unit=68%/32%, acid anhydride group concentration: 1.18 mmol/g, water Average molecular weight: 4,500)

T-YP432 (manufactured by Seiko 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 Seiko PMC): maleic anhydride modified styrene-isobutylene-styrene copolymer (styrene unit/isobutylene unit=20%/80%, acid anhydride group concentration: 0.464 mmol/g, water Average molecular weight: 35,800)

T-YP8930 (manufactured by Seiko 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 (manufactured by Seiko 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 (manufactured by Seiko 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 Seiko 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 Co., Ltd.): Maleic anhydride-modified liquid polybutene (acid anhydride group concentration: 0.77 mmol/g, number average molecular weight: 2,100)

·HV-1900 (manufactured by JX Energizer): polybutene (number average molecular weight: 2,900)

(B) metal hydroxide

・DHT-4C (manufactured by Kyowa Chemical 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 Co., Ltd.): semi-calcined hydrotalcite (average particle diameter: 400 nm, BET specific surface area: 10 m ² /g)

・DHT-4A (manufactured by Kyowa Chemical Co., Ltd.): hydrotalcite (average particle diameter: 400 nm, BET specific surface area: 10 m ² /g)

(B') Hygroscopic metal oxide

· KW2200 (manufactured by Kyowa Chemical Co., Ltd.): Calcined hydrotalcite (average particle diameter: 400 nm, BET specific surface area: 129 m ² /g)

・N41S: Calcined hydrotalcite (manufactured by Todakogyo Co., Ltd.) (average particle diameter: 40 nm, BET specific surface area: 133 m ² /g)

Moistop #10 (manufactured by Sankyo Seifun Corporation): Calcium oxide (average particle diameter: 4㎛, BET specific surface area: 5m ² /g)

・FNM-G (manufactured by Dateho Chemical 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): Hydrogenated petroleum resin containing cyclohexane ring (softening point 125°C)

(D) Hardener

·Amine-based hardener (2,4,6-tris(diaminomethyl)phenol, hereinafter abbreviated as “TAP”)

organic solvent

·toluene

· Swasol #1000 (manufactured by Maruzenseki Yu Co., Ltd.): Aromatic mixed solvent

Each composition of Examples and Comparative Examples was prepared in the order shown below. Mixing was carried out in the amounts shown in Tables 1 and 2. In addition, the amounts of components other than the organic solvent shown in Table 1 and Table 2 are values converted into non-volatile content.

<Example 1>

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

<Example 2>

Varnish and sealing sheets of the resin composition were produced in the same manner as in Example 1, except that the amount of semi-baked hydrotalcite (DHT-4C) used was changed from 100 parts to 80 parts.

<Example 3>

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

<Example 4>

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

<Example 5>

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

<Example 6>

Instead of maleic anhydride modified ethylene-methylmethacrylate copolymer (T-YP429, 20% toluene solution), an equivalent amount of maleic anhydride modified styrene-isobutylene-styrene copolymer (T-YP8920, 20% toluene solution) was used. Instead of using glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (T-YP431, 20% toluene solution), an equal amount of glycidyl methacrylate-modified styrene-isobutylene-styrene copolymer was used. A varnish and sealing sheet of the resin composition were produced in the same manner as in Example 1, except that a polymer (T-YP8930, 20% toluene solution) was used.

<Example 7>

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

<Example 8>

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

<Comparative Example 1>

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

<Comparative Example 2>

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

<Comparative Example 3>

Varnish and sealing sheets of the resin composition were produced in the same manner as Example 1, except that calcium oxide (Moistop #10) was used instead of semi-baked hydrotalcite (DHT-4C).

<Comparative Example 4>

A varnish and sealing sheet of the resin composition was produced in the same manner as Example 1, except that magnesium oxide (FNM-G) was used instead of semi-baked hydrotalcite (DHT-4C).

The resin composition layers of the sealing 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 permeability resistance (water vapor permeation amount)

The water vapor permeation amount per 1 m ² of the resin composition layer (thickness: 45 μm) peeled from the support (PET film) of the sealing sheet produced in Examples and Comparative Examples was measured in accordance with JIS Z0208 at a temperature of 40°C and a humidity of 90%. It was measured under conditions of % RH and 24 hours, and evaluated based on the following criteria. The results are listed in Table 1.

Good (○): Water vapor permeability is less than 10g/m ² 24hr

Possible (△): Water vapor permeability greater than 10g/m ² 24hr, less than 20g/m ² 24hr

Defective (×): Water vapor permeability is more than 20g/ ^m2 ·24hr

2. Evaluation of total light transmittance

The sealing sheet (thickness of the resin composition layer: 20 μm) prepared in the examples and comparative examples was cut into 50 mm in length and 20 mm in width, and the cut sealing sheet was placed on a glass plate (microslide glass with a length of 76 mm, a width of 26 mm, and a thickness of 1.2 mm). , white slide glass S1112 polished No. 2 manufactured by Matsunami Glass Co., Ltd. was laminated using a batch type vacuum laminator (V-160 manufactured by Nichigo Moton Corporation). Laminate conditions were a temperature of 80°C, a decompression time of 30 seconds, and then pressurization at a pressure of 0.3 MPa for 30 seconds. After that, the PET film of the sealing sheet was peeled off, and a glass plate as described above was additionally laminated on the exposed cured resin composition layer to produce a laminate. The light transmittance spectrum of the obtained laminate was measured externally using a fiber-type spectrophotometer (MCPD-7700, type 311C, manufactured by Otsuka Electronics Co., Ltd.) equipped with an integrating sphere (model name SRS-99-010, reflectance 99%) of 80 mm. Light source unit: measured using a halogen lamp MC-2564 (24V, 150W specification)), the total light transmittance at a wavelength of 450 nm was calculated, and evaluated based on the following criteria. Additionally, the distance between the integrating sphere and the sample (laminated body) was set to 0 mm, and glass was used as a reference.

Good (○): 95% or more

Possible (△): 90% or more, less than 95%

Defective (×): Less than 90%

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

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

This application is based on Japanese Patent Application No. 2015-193115 filed in Japan, the entire contents of which are included in the specification of this application.

Claims (14)

(A) polyolefin-based resin, and
(B) a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite.
A resin composition for sealing containing,
(A) A resin composition for sealing 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 for sealing according to claim 1, wherein (A) the polyolefin resin includes a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group. The resin composition for sealing according to claim 2, which has a crosslinked structure formed by reaction of an acid anhydride group and an epoxy group. The resin composition for sealing according to any one of claims 1 to 3, which is a pressure-sensitive adhesive. (A) polyolefin-based resin, and
(B) a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite.
A resin composition for sealing, which is a pressure-sensitive adhesive comprising. The resin composition for sealing according to any one of claims 1 to 3 or 5, further comprising (C) a tackifying resin. The resin composition for sealing according to any one of claims 1 to 3 or 5, further comprising (D) a curing agent. The resin composition for sealing according to any one of claims 1 to 3 or 5, which is used for sealing an organic EL element. The resin composition for sealing according to any one of claims 1 to 3 or 5, wherein the total light transmittance (parallel transmittance) of the resin composition layer for sealing with a thickness of 20 μm is 90% or more at a wavelength of 450 nm. A sealing sheet in which a sealing resin composition layer made of the sealing resin composition according to any one of claims 1 to 3 or 5 is formed on one or both surfaces of a support. The method of claim 10, wherein (A) the polyolefin resin includes a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group, and the sealing resin composition layer has a crosslinked structure formed by reaction of the acid anhydride group and the epoxy group. A sealing sheet having. The sealing sheet according to claim 11, which is used for sealing organic EL elements. An organic EL device comprising an organic EL element sealed with the resin composition for sealing according to any one of claims 1 to 3 or 5. An organic EL device comprising an organic EL element sealed with the sealing sheet according to claim 11.