WO2016158770A1 - Resin composition for sealing - Google Patents

Resin composition for sealing Download PDF

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Publication number
WO2016158770A1
WO2016158770A1 PCT/JP2016/059664 JP2016059664W WO2016158770A1 WO 2016158770 A1 WO2016158770 A1 WO 2016158770A1 JP 2016059664 W JP2016059664 W JP 2016059664W WO 2016158770 A1 WO2016158770 A1 WO 2016158770A1
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WO
WIPO (PCT)
Prior art keywords
resin
sealing
resin composition
modified
copolymer
Prior art date
Application number
PCT/JP2016/059664
Other languages
French (fr)
Japanese (ja)
Inventor
舞 高瀬
有希 山本
達也 本間
中嶋　聡
英治 馬場
賢 大橋
Original Assignee
味の素株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 味の素株式会社 filed Critical 味の素株式会社
Priority to JP2017509913A priority Critical patent/JP6680295B2/en
Priority to CN201680016320.3A priority patent/CN107406639B/en
Priority to KR1020177030477A priority patent/KR102522727B1/en
Publication of WO2016158770A1 publication Critical patent/WO2016158770A1/en

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/842—Containers
    • H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C08L2203/162—Applications used for films sealable films

Definitions

  • the present invention relates to an encapsulating resin composition, an encapsulating sheet, and the like, and more particularly to an encapsulating resin composition and an encapsulating sheet that can be suitably used for encapsulating an organic EL element.
  • An organic EL (Electroluminescence) element is a light-emitting element using an organic substance as a light-emitting material, and has been attracting attention in recent years because it can emit light with high luminance at a low voltage.
  • the organic EL element is extremely vulnerable to moisture, and the organic material itself is altered by moisture, resulting in a decrease in brightness, no light emission, or the interface between the electrode and the organic EL layer being peeled off due to moisture, Since there is a problem that the metal is oxidized to increase the resistance, the organic EL element is sealed.
  • thermosetting resin composition When the thermosetting resin composition is used as a sealing material for the entire surface of a substrate having an organic EL element, the laminating work is easy because the material viscosity before curing is low, and the permeation resistance of the cured product after thermosetting is low. An advantage is high wetness. However, on the other hand, there is a problem that the organic EL element deteriorates due to the heating temperature during thermosetting.
  • Patent Document 1 discloses sealing with a polyisobutylene resin, a polyisoprene resin having a functional group capable of reacting with an epoxy group and / or a polyisobutylene resin, a tackifying resin, and a resin composition containing an epoxy resin.
  • Patent Document 2 discloses a technique of sealing with a resin composition containing a styrene-isobutylene-modified resin and a tackifier resin.
  • the problem to be solved by the present invention is to provide a sealing resin composition excellent in adhesion wet heat resistance and moisture permeability resistance.
  • the present inventor has (A) (meth) acrylic acid alkyl ester and polyolefin-based resin modified with acid anhydride, (B) epoxy resin, and (C) tackifying resin.
  • a sealing resin composition characterized by containing a pressure-sensitive adhesive composition having a good cross-linking structure formed by heating before sealing, and having excellent resistance to moisture and heat resistance and moisture permeability.
  • the headline and the present invention were completed.
  • a sealing resin comprising (A) a (meth) acrylic acid alkyl ester and a polyolefin-based resin modified with an acid anhydride, (B) an epoxy resin, and (C) a tackifying resin. Composition.
  • (A) An ester bond formed by reacting an acid anhydride group of a polyolefin resin modified with (meth) acrylic acid alkyl ester and acid anhydride and an epoxy group of (B) epoxy resin is formed.
  • a sealing sheet. [12] The sealing sheet according to [11], which is used for sealing an organic EL element.
  • a resin varnish containing the sealing resin composition according to any one of the above [1] to [9] is applied onto a support and heat-dried, and (A) an alkyl (meth) acrylate Production of a sealing sheet, wherein an acid anhydride group of a polyolefin-based resin modified with an ester and an acid anhydride and an epoxy group of (B) an epoxy resin are ester-bonded by reaction to form an adhesive layer Method.
  • the sealing resin composition excellent in the adhesion heat-and-moisture resistance and moisture permeability resistance, the sealing sheet obtained from it, and the organic EL device sealed with this sealing resin composition are provided. Is done.
  • the encapsulating resin composition of the present invention (hereinafter also simply referred to as “resin composition”) is (A) a polyolefin-based resin modified with (meth) acrylic acid alkyl ester and acid anhydride, and (B) epoxy.
  • resin composition is (A) a polyolefin-based resin modified with (meth) acrylic acid alkyl ester and acid anhydride, and (B) epoxy.
  • the main feature is that it contains a resin and (C) a tackifying resin.
  • the resin composition of the present invention includes a polyolefin resin modified with a (meth) acrylic acid alkyl ester and an acid anhydride (hereinafter sometimes referred to as “modified polyolefin resin” or “(A) component”). Is used.
  • the polyolefin resin of the main skeleton of the modified polyolefin resin used in the present invention is not particularly limited as long as it has a skeleton derived from an olefin monomer.
  • a polyethylene resin, a polypropylene resin, a polybutene resin, a polyisobutylene resin, and the like can be given.
  • polyethylene resins, polypropylene resins, and polybutene resins are preferable, and polyethylene resins and polypropylene resins are particularly preferable.
  • the polyethylene-based resin referred to here is a homopolymer of ethylene or a main monomer unit (a monomer unit of more than 50% by mass) made of ethylene. At least ethylene and a unit other than ethylene are used. It means a copolymer containing a monomer unit (for example, a monomer unit such as an olefin excluding ethylene, a non-conjugated diene, an alkyl (meth) acrylate), and the polypropylene resin is a homopolymer of propylene, Alternatively, the main monomer unit (a monomer unit of more than 50% by mass) is composed of propylene, at least propylene and monomer units other than propylene (for example, olefins other than propylene, non-conjugated dienes, (meth)
  • a polybutene-based resin is a homopolymer of butene, or Is a main monomer unit (a monomer unit of more than 50% by mass) consisting
  • a monomer unit other than isobutylene eg, a monomer unit such as an olefin excluding isobutylene, a non-conjugated diene, or a (meth) acrylic acid alkyl ester.
  • the polyethylene resin is superior to the polypropylene resin.
  • “processability” refers to processability particularly when a modified polyolefin resin is formed on a film (layer), and the fluidity of the resin varnish to enable film (layer) formation (time-lapse). Stability) and the like.
  • polypropylene resin is superior to polyethylene resin.
  • the copolymer includes (i) a copolymer of two or more olefins, (ii) a copolymer of olefin and non-conjugated diene, or (iii) a monomer other than olefin such as olefin and styrene (non-conjugated diene). And a copolymer thereof.
  • the olefin can use 1 type (s) or 2 or more types.
  • copolymer in the polyolefin resin examples include, for example, ethylene-nonconjugated diene copolymer, ethylene- (meth) acrylic acid alkyl ester copolymer, ethylene-butene copolymer, ethylene-butene-nonconjugated.
  • any copolymer may be a random copolymer or a block copolymer.
  • the block copolymer may be a diblock copolymer or a triblock copolymer.
  • an ethylene-butene copolymer block copolymer is a diblock copolymer (polyethylene block (polyethylene skeleton) -polybutene block (polybutene skeleton)) consisting of a multi-block consisting of alternating repeating polyethylene blocks and polybutene blocks.
  • Block copolymer polyethylene block (polyethylene skeleton) -polybutene block (polybutene skeleton) -triblock copolymer consisting of polyethylene block (polyethylene skeleton), polybutene block (polybutene skeleton) -polyethylene block (polyethylene skeleton)- A triblock copolymer comprising a polybutene block (polybutene skeleton) is included. The same applies to binary copolymers other than ethylene-butene copolymers.
  • polyethylene resin for example, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-butene copolymer and the like can be used from the viewpoint of improving heat resistance and the like.
  • propylene-based resin for example, from the viewpoint of improving processability and embedding property, a propylene-ethylene copolymer, a propylene-butene copolymer, and an ethylene-propylene-butene copolymer can be used. Further, from the viewpoint of improving heat resistance, a propylene-butene copolymer can be used.
  • the butene used in the present invention is not particularly limited, and can include 1-butene, cis-2-butene, trans-2-butene, isobutene (other name: 2-methylpropene), and the like. Two or more types can be used in combination, but 1-butene is preferred.
  • the ethylene-butene copolymer may be a copolymer obtained by copolymerizing ethylene and two or more types of butene, or the butene units are different from each other. It may be a mixture of two or more ethylene-butene copolymers comprising butene.
  • the form of the ethylene-butene copolymer is not particularly limited, and may be a random copolymer or a block copolymer. Among them, from the viewpoint of improving processability, the random copolymer is used. Polymers are preferred.
  • olefins that may be included as monomer units of polyolefin resins (that is, olefins other than ethylene, propylene, butene, and isobutylene) include 1-pentene, 3-methyl-1-hexene, 3-methyl ⁇ having 2 to 11 carbon atoms, such as -1-pentene, 4-methyl-1-pentene, 3-ethyl-1-pentene, 1-septene, 1-octene, 1-nonene, 1-decene, 1-undecene, etc. Mention may be made of olefins (excluding propylene and 1-butene). Of these, 1-hexene is preferable. Such ⁇ -olefins can be used alone or in combination of two or more.
  • olefins having a carbon number such as methylhexadiene (2-methyl-1,5-hexadiene, 3-methyl-2,4-hexadiene, etc.), 1,9-decadiene, 1,13-tetradecadiene, etc.
  • methylhexadiene is preferable, and 2-methyl-1,5-hexadiene is particularly preferable.
  • non-conjugated diolefin compounds can be used alone or in combination of two or more.
  • a copolymer of olefin and (meth) acrylic acid alkyl ester can be used as the polyolefin resin of the main skeleton in the modified polyolefin resin of the present invention.
  • (meth) acrylic acid alkyl ester means acrylic acid alkyl ester and methacrylic acid alkyl ester. Either one or both of acrylic acid alkyl ester and methacrylic acid alkyl ester may be used.
  • the alkyl group in the (meth) acrylic acid alkyl ester may be an unsubstituted alkyl group or a substituted alkyl group (for example, an aralkyl group), but an unsubstituted alkyl group is preferred.
  • the group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
  • (meth) acrylic acid alkyl esters include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl hexyl acrylate, isobutyl acrylate, benzyl acrylate, phenoxyethyl acrylate, methyl methacrylate, methacrylic acid Examples include ethyl, butyl methacrylate, ethyl hexyl methacrylate, isobutyl methacrylate, benzyl methacrylate, and phenoxyethyl methacrylate. Of these, methyl methacrylate is preferred.
  • One or more (meth) acrylic acid alkyl esters can be used.
  • a copolymer containing at least butene as a monomer unit such as an ethylene-butene copolymer, an isobutylene-butene copolymer, and a propylene-butene copolymer
  • ethylene-butene copolymer an ethylene-butene copolymer
  • isobutylene-butene copolymer an isobutylene-butene copolymer
  • a propylene-butene copolymer is a resin composition.
  • the content of ethylene units is preferably 20% by mass or more based on the whole copolymer, 30 mass% or more is more preferable, 40 mass% or more is still more preferable, and 50 mass% or more is the most preferable.
  • 95% by mass or less is preferable, and 90% by mass or less is more preferable.
  • ethylene- (meth) acrylic acid alkyl ester copolymer In the modified polyolefin resin of the present invention, ethylene- (meth) acrylic acid alkyl ester copolymer, isobutylene- (meth) acrylic acid alkyl ester copolymer, propylene- (meth) acrylic acid alkyl ester copolymer, etc.
  • the copolymer of olefin and (meth) acrylic acid alkyl ester which contains at least (meth) acrylic acid alkyl ester as a monomer unit, has a balance of performance such as adhesion and moisture resistance of the resin composition.
  • the content of ethylene units is preferably 30% by mass or more, more preferably 40% by mass or more, based on the entire copolymer, 50% The mass% or more is even more preferable. For the same reason, 95% by mass or less is preferable, and 90% by mass or less is more preferable.
  • ethylene-butene copolymer, propylene-butene copolymer, isobutylene-butene copolymer, etc. are further copolymerized with other olefins other than ethylene, propylene, isobutylene and butene.
  • ethylene-butene copolymer, propylene-butene copolymer, isobutylene-butene copolymer, etc. are further copolymerized with other olefins other than ethylene, propylene, isobutylene and butene.
  • the ratio of the other olefin units is such that the ethylene unit, butene unit and other
  • the total amount of olefin units, the total amount of propylene units, butene units and other olefin units, or the total amount of isobutylene units, butene units and other olefin units is preferably 20% by mass or less, more preferably 10% by mass or less. Preferably, 5% by mass or less is particularly preferable, and 3% by mass or less is most preferable.
  • ethylene- (meth) acrylic acid alkyl ester copolymer In the modified polyolefin resin of the present invention, ethylene- (meth) acrylic acid alkyl ester copolymer, isobutylene- (meth) acrylic acid alkyl ester copolymer, propylene- (meth) acrylic acid alkyl ester copolymer, etc.
  • ethylene- (meth) acrylic acid alkyl ester copolymer isobutylene- (meth) acrylic acid alkyl ester copolymer
  • propylene- (meth) acrylic acid alkyl ester copolymer etc.
  • a copolymer in which other olefins other than ethylene, propylene and isobutylene are further copolymerized is used, in order to take advantage of the characteristics of the ethylene unit, propylene unit, isobutylene unit, etc.
  • the proportion of olefin units is the total amount of ethylene units, (meth) acrylic acid alkyl ester units and other olefin units, propylene units, (meth) acrylic acid alkyl ester units and other olefin units, or isobutylene units ( (Meth) acrylic acid alkyl ester butene unit
  • the total amount of other olefin units preferably 20 wt% or less, more preferably 10 wt% or less, especially preferably 5 mass% or less, and most preferably 3 wt% or less.
  • the modified polyolefin resin in the present invention is one in which a polyolefin resin is modified with a (meth) acrylic acid alkyl ester and an acid anhydride from the viewpoint of imparting excellent physical properties such as adhesion moisture heat resistance and moisture resistance. That is, the modified polyolefin resin in the present invention is a graft modified product in which a graft chain containing a unit derived from (meth) acrylic acid alkyl ester and a unit derived from an acid anhydride is bonded to the main chain of the polyolefin resin.
  • the (meth) acrylic acid alkyl ester here means an acrylic acid alkyl ester or a methacrylic acid alkyl ester, and each may be used alone, or a mixture of an acrylic acid alkyl ester and a methacrylic acid alkyl ester. Also good.
  • the number of carbon atoms of the alkyl group in the (meth) acrylic acid alkyl ester is preferably 1 to 18, more preferably 1 to 14, still more preferably 1 to 12, particularly preferably 1 to 10, and most preferably 1 to 8. .
  • Specific examples of (meth) acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, and 2-butyl acrylate.
  • 2-ethylhexyl acrylate, n-butyl methacrylate and the like are preferable, and 2-ethylhexyl acrylate is more preferable.
  • One or more (meth) acrylic acid alkyl esters can be used.
  • acid anhydride examples include succinic anhydride, maleic anhydride, glutaric anhydride, and the like. Particularly preferred is succinic anhydride.
  • One or more acid anhydrides can be used.
  • Polyolefin resins modified with (meth) acrylic acid alkyl esters and acid anhydrides include, for example, polyolefin resins, unsaturated compounds having acid anhydride groups and alkyl (meth) acrylates under radical reaction conditions. It can be obtained by graft modification with an ester (see, for example, JP-A Nos. 2002-173514 and 2006-219627).
  • the number average molecular weight of the graft chain (graft polymer) formed from the (meth) acrylic acid alkyl ester and the acid anhydride is preferably 100 or more, more preferably 200 or more, still more preferably 300 or more.
  • a graft chain having an appropriate length tends not to be formed.
  • the average value of the number average molecular weight of the graft chain (graft polymer) is too small, it tends to be difficult to form a crosslinked structure with an epoxy resin, particularly an epoxy-modified polyolefin resin.
  • the upper limit of the average value of the number average molecular weight of the graft chain (graft polymer) is not particularly limited as long as the functions of the resin composition of the present invention such as sealing performance, adhesion heat resistance, moisture resistance, etc. are exhibited. Is 5000 or less, preferably 3000 or less.
  • the graft chain (graft polymer) preferably contains (meth) acrylic acid alkyl ester units in an amount of 20 wt% to 80 wt%, more preferably 30 wt% to 70 wt%, more preferably 40 wt%. More preferably, the content is 60% by weight or less.
  • the number average molecular weight of the graft chain (graft polymer) can be determined by measuring the molecular weight by the viscosity of the graft modified product, chemical structure analysis of the graft modified product, gel permeation chromatography (GPC) method (polystyrene conversion), and the like.
  • GPC gel permeation chromatography
  • the molecular weight of the polymer component formed only from the added (meth) acrylic acid alkyl ester and acid anhydride, which is not bonded to the main chain of the polyolefin resin, is measured by the GPC method or the like. This can be easily obtained.
  • the number average molecular weight by the GPC method is specifically determined by moving LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex® K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column. Using toluene or the like as a phase, the measurement can be made at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.
  • a component may be used 1 type or may mix and use 2 or more types. That is, two or more types of graft-modified products having different main-framework polyolefin resins and / or graft polymers can be mixed and used.
  • the concentration and number average molecular weight of the acid anhydride group of the component (A) described below are values in the entire mixture of two or more types of graft-modified products.
  • the number average molecular weight of the graft chain (graft polymer) is also the number average molecular weight of the total graft polymer of the mixture.
  • the concentration of the acid anhydride group in the component (A) is preferably 0.05 to 10 mmol / g, and more preferably 0.1 to 5 mmol / g.
  • the concentration of the acid anhydride group is obtained from the value of the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of resin according to the description of JIS K2501.
  • the number average molecular weight of the component (A) is not particularly limited, but is preferably 500,000 or less from the viewpoint of providing good coatability of the varnish of the resin composition and good compatibility with other components in the resin composition. 300000 or less is more preferable, and 150,000 or less is still more preferable. On the other hand, it is preferably 10,000 or more, more preferably 30000 or more from the viewpoint of preventing repelling during coating of the varnish of the resin composition, expressing moisture resistance of the formed resin composition layer, and improving mechanical strength. Preferably, 50000 or more is more preferable.
  • the number average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion).
  • the number average molecular weight by the GPC method is specifically determined by moving LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex® K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column. Using toluene or the like as a phase, the measurement can be made at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.
  • the component (A) is preferably low in crystallinity and particularly preferably noncrystalline from the viewpoint of improving workability.
  • non-crystalline means that the component (A) does not have a clear melting point.
  • DSC differential scanning calorimetry
  • (A) component in the resin composition of this invention brings about the favorable coating property and compatibility of the varnish of a resin composition, and favorable wet heat in the resin composition layer formed From the viewpoint of ensuring resistance and handleability (tack suppression), when the nonvolatile content in the resin composition is 100% by mass, it is preferably 45% by mass or less, more preferably 40% by mass or less, and 35% by mass or less. Further preferred. On the other hand, from the viewpoint of improving moisture permeability and improving transparency, when the nonvolatile content in the resin composition is 100% by mass, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 15% by mass. % Or more is more preferable.
  • the resin composition of the present invention contains an epoxy resin (hereinafter also abbreviated as “component (B)”).
  • An epoxy resin forms a crosslinked structure by reaction with the acid anhydride group which (A) component has.
  • the epoxy resin is not particularly limited as long as it has an average of two or more epoxy groups per molecule.
  • bisphenol A type epoxy resin for example, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine Type epoxy resin (for example, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyltoluidine, diglycidylaniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac Type epoxy resin, bisphenol A novolac type epoxy resin, epoxy resin containing polyalkylene glycol skeleton, epoxy resin having butadiene structure, bisphenol And diglycidyl etherified products of naphthalenediol, glycidyl etherified products of phenols, digly
  • epoxy resins bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy resin, aromatic glycidyl amine type epoxy resin, dicyclopentadiene structure
  • An epoxy resin, a polypropylene glycol skeleton-containing epoxy resin, and the like are preferable, and a bisphenol A type epoxy resin and a polypropylene glycol skeleton-containing epoxy resin are particularly preferable.
  • epoxy resins include “828EL” (liquid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “HP4032”, “HP4032D” (all naphthalene type bifunctional epoxy resins) manufactured by DIC, and “ “HP4700” (naphthalene type tetrafunctional epoxy resin), DIC's "HP7200 series” (dicyclopentadiene type epoxy resin), Toto Kasei's “ESN-475V”, “ESN-185V” (all naphthol type epoxy resins) “PB-3600” (epoxy resin having a butadiene structure) manufactured by Daicel Chemical Industries, Ltd., “NC3000H”, “NC3000L”, “NC3100”, “NC3000”, “NC3000FH-75M” manufactured by Nippon Kayaku Co., Ltd.
  • the epoxy resin may be liquid or solid, and both liquid and solid may be used.
  • “liquid” and “solid” are states of the epoxy resin at room temperature (25 ° C.).
  • the component (B) preferably has an epoxy equivalent of 100 to 1500 g / eq, more preferably 150 to 1000 g / eq, and still more preferably 200 to 800 g / eq.
  • the “epoxy equivalent” is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method defined in JIS K 7236.
  • an epoxy-modified polyolefin resin that is, a polyolefin resin having an epoxy group is particularly preferable.
  • the epoxy-modified polyolefin resin include a graft-modified product in which a graft polymer containing a unit of an epoxy group-containing unsaturated compound is bonded to the main chain of the polyolefin resin.
  • the graft-modified product can be obtained by graft-modifying a polyolefin resin with an epoxy group-containing unsaturated compound under radical reaction conditions.
  • Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, 2-hydroxyethyl acrylate glycidyl ether, and allyl glycidyl ether. Preferably, it is glycidyl methacrylate. These can use 1 type (s) or 2 or more types.
  • Specific examples of the polyolefin-based resin in the graft-modified product include the same as those exemplified as specific examples of the polyolefin-based resin in the component (A).
  • the epoxy-modified polyolefin-based resin one or two or more kinds selected from the above epoxy group-containing unsaturated compounds and one or two or more olefins are radically copolymerized to obtain an epoxy group-containing unsaturated resin. You may make it obtain as a copolymer containing a compound unit and an olefin unit.
  • Specific examples of the olefin include the same examples as the constituent monomer units of the polyolefin resin having the main skeleton in the modified polyolefin resin of the component (A).
  • the concentration of the epoxy group in the epoxy-modified polyolefin resin is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g.
  • the epoxy group concentration is determined from the epoxy equivalent obtained based on JIS K 7236-1995.
  • the number average molecular weight of the epoxy-modified polyolefin resin is not particularly limited, but from the viewpoint of providing good coatability of the varnish of the resin composition and good compatibility with other components in the resin composition, it is 500,000 or less. Preferably, 300,000 or less is more preferable, and 150,000 or less is still more preferable. On the other hand, it is preferably 10,000 or more, more preferably 30000 or more from the viewpoint of preventing repelling during coating of the varnish of the resin composition, expressing moisture resistance of the formed resin composition layer, and improving mechanical strength. Preferably, 50000 or more is more preferable. In addition, the number average molecular weight here is measured by a gel permeation chromatography (GPC) method (polystyrene conversion).
  • GPC gel permeation chromatography
  • the number average molecular weight by the GPC method is specifically determined by moving LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex® K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column. Using toluene or the like as a phase, the measurement can be made at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.
  • the epoxy-modified polyolefin-based resin preferably has low crystallinity from the viewpoint of improving processability, and is particularly preferably amorphous.
  • non-crystalline means that the epoxy-modified polyolefin resin does not have a clear melting point, for example, when the melting point is measured by DSC (differential scanning calorimetry) of the epoxy-modified polyolefin resin. A clear peak is not observed.
  • (B) Component may be used alone or in combination of two or more.
  • limiting in particular in content of (B) component in a resin composition From a viewpoint that favorable moisture-permeable resistance can be ensured, when the non volatile matter in a resin composition is 100 mass%, it is 45 mass% or less. Is preferable, 40 mass% or less is more preferable, and 35 mass% or less is still more preferable.
  • the nonvolatile content in the resin composition is 100% by mass, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 15% by mass. The above is more preferable.
  • the amount ratio of the component (A) and the component (B) in the resin composition of the present invention is arbitrarily selected within the range in which the effect of the present invention is exerted, but forms a good cross-linked structure and unreacted activity. From the viewpoint of reducing the content of functional groups and exhibiting performance stably, the ratio of the acid anhydride equivalent (Ea) of the component (A) to the epoxy equivalent (Eb) of the component (B) (Ea / Eb) However, the ratio is preferably 0.7 to 1.45, more preferably 0.8 to 1.25, still more preferably 0.9 to 1.15, and still more preferably 0.95 to 1.06.
  • the “acid anhydride equivalent” is the number of grams (g / eq) of a resin containing 1 gram equivalent of an acid anhydride group.
  • the total content of the component (A) and the component (B) is not particularly limited, but from the viewpoint of adhesiveness, workability, etc., the nonvolatile content in the resin composition is 100% by mass. 80 mass% or less is preferable, 75 mass% or less is more preferable, and 70 mass% or less is still more preferable. On the other hand, from the viewpoint of wet heat resistance, when the nonvolatile content in the resin composition is 100% by mass, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 15% by mass or more is even more preferable.
  • the (C) tackifier resin (hereinafter also abbreviated as “component (C)”) used in the present invention is also called a tackifier and is a resin that is added to a plastic polymer to impart tackiness.
  • the component (C) is not particularly limited, and includes terpene resins, modified terpene resins (hydrogenated terpene resins, terpene phenol copolymer resins, aromatic modified terpene resins, etc.), coumarone resins, indene resins, petroleum resins ( Aliphatic petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene petroleum resins and their hydrides) Preferably used.
  • terpene resins modified terpene resins (hydrogenated terpene resins, terpene phenol copolymer resins, aromatic modified terpene resins, etc.), coumarone resins, indene resins, petroleum resins ( Aliphatic petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins,
  • terpene resin aromatic modified terpene resin, terpene phenol copolymer resin, hydrogenated alicyclic petroleum resin, aromatic petroleum resin, Aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins are more preferred, alicyclic petroleum resins are more preferred, alicyclic saturated hydrocarbon resins are even more preferred, cyclohexane ring-containing saturated hydrocarbon resins, Dicyclopentadiene-modified hydrocarbon resin is particularly preferred.
  • component (C) examples include terpene resins such as YS resin PX and YS resin PXN (both manufactured by Yasuhara Chemical Co., Ltd.), and aromatic-modified terpene resins such as YS resin TO and TR series (any Are Yasuhara Chemical Co., Ltd.), and hydrogenated terpene resins include Clearon P, Clearon M, Clearon K series (all manufactured by Yasuhara Chemical Co., Ltd.), and terpene phenol copolymer resins are YS Polystar 2000, Polystar U.
  • alicyclic petroleum resins include Escorez 5300 series, 5600 series (all manufactured by ExxonMobil Corp.), etc. Tribe oil tree ENDEX155 (manufactured by Eastman Co., Ltd.) and the like, quintone D100 (manufactured by Nippon Zeon Co., Ltd.) and the like as aliphatic aromatic copolymer petroleum resins, and quintone 1325 and quintone 1345 (both from Nippon Zeon) as alicyclic petroleum resins.
  • Tribe oil tree ENDEX155 manufactured by Eastman Co., Ltd.
  • quintone D100 manufactured by Nippon Zeon Co., Ltd.
  • quintone 1325 and quintone 1345 both from Nippon Zeon
  • Alcon P100, Alcon P125, Alcon P140 (all manufactured by Arakawa Chemical Co., Ltd.) and the like are listed as hydrogenated alicyclic petroleum resins, and TFS13-030 (Arakawa) is a cyclohexane ring-containing saturated hydrocarbon resin. Chemical Co., Ltd.).
  • the softening point of the component (C) is preferably from 50 to 200 ° C., more preferably from 90 to 180 ° C., from the viewpoint that the sheet softens in the resin composition sheet lamination step and has the desired heat resistance. 150 ° C. is more preferable.
  • the softening point is measured by the ring and ball method according to JIS K2207.
  • the content of the component (C) in the resin composition is not particularly limited, but from the viewpoint of maintaining good moisture resistance of the resin composition, when the nonvolatile content in the resin composition is 100% by mass, 80 mass% or less is preferable, 60 mass% or less is more preferable, and 50 mass% or less is still more preferable. On the other hand, from the viewpoint of having sufficient adhesiveness, when the nonvolatile content in the resin composition is 100% by mass, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 15% by mass or more is even more preferable.
  • the resin composition for sealing containing the polyolefin resin which has an acid anhydride group and / or an epoxy group, and tackifying resin, Preferably, it has the polyolefin resin which has an acid anhydride group, and an epoxy group
  • An encapsulating resin composition containing a polyolefin-based resin and a tackifying resin is exemplified.
  • the polyolefin resin having an acid anhydride group is not particularly limited as long as it is a resin having an acid anhydride group by acid anhydride modification, and is modified with the (meth) acrylic acid alkyl ester and acid anhydride of the component (A).
  • polyolefin-based resin May be a polyolefin-based resin, and may contain other functional groups by other modifications. That is, the “polyolefin resin having an acid anhydride group” is characterized in that the (meth) acrylic acid alkyl ester of the component (A) and the acid are other than that the (meth) acrylic acid alkyl ester modification is not essential.
  • polyolefin resin modified with anhydride the polyolefin resin may be a copolymer, and specific examples of the copolymer include, for example, an ethylene-nonconjugated diene copolymer, an ethylene-butene copolymer, and an ethylene-butene-nonconjugated diene copolymer.
  • tackifying resin is synonymous with the tackifying resin of the said (C) component.
  • the functional group concentration of the acid anhydride group and / or epoxy group of the polyolefin resin having an acid anhydride group and / or epoxy group is preferably 0.05 to 10 mmol / g.
  • the content of the propylene-butene copolymer having an acid anhydride group and / or an epoxy group is preferably 35 to 80% by mass per 100% by mass of the total nonvolatile content in the resin composition.
  • the sealing resin composition here can preferably be used for sealing organic EL elements.
  • the resin composition for sealing materials here is in the form of a sealing sheet and can be used, for example, for organic EL sealing.
  • the resin composition of the present invention (resin composition containing the above components (A) to (C)) and the resin composition of the above reference examples further contain a curing accelerator from the viewpoint of forming a good crosslinked structure. You may let them. Although it does not specifically limit as a hardening accelerator, An amine hardening accelerator, a guanidine hardening accelerator, an imidazole hardening accelerator, a phosphonium hardening accelerator, etc. are mentioned. You may use a hardening accelerator 1 type or in combination of 2 or more types.
  • the amine curing accelerator is not particularly limited, but includes quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide; DBU (1,8-diazabicyclo [5.4.0] undecene-7), DBN (1,5-diazabicyclo [4.3.0] nonene-5), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, DBU-phenol novolac resin salt, etc.
  • 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
  • the guanidine curing accelerator is not particularly limited, but dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.
  • dec-5-ene 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1- Cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide And 1- (o-tolyl) biguanide. You may use these 1 type or in combination of 2 or more types.
  • the imidazole curing accelerator is not particularly limited, but 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl-imidazole, 2-phenyl- 4,5-bis (hydroxymethyl) -imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-imidazole, 2-dodecyl-imidazole 2-heptadecylimidazole, 1,2-dimethyl-imidazole and the like. You may use these 1 type or in combination of 2 or more types.
  • the phosphonium curing accelerator is not particularly limited, but triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) Examples include triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. You may use these 1 type or in combination of 2 or more types.
  • the curing accelerator may be used alone or in combination of two or more.
  • limiting in particular in content of the hardening accelerator in a resin composition From a viewpoint of preventing the fall of moisture permeability resistance, when the non volatile matter in a resin composition is 100 mass%, 5 mass% or less is Preferably, 1 mass% or less is more preferable.
  • from the viewpoint of suppressing tackiness when the nonvolatile content in the resin composition is 100% by mass, 0.01% by mass or more is preferable, and 0.05% by mass or more is more preferable.
  • the resin composition of the present invention can further contain a hygroscopic metal oxide in order to further improve the moisture permeability resistance.
  • the “hygroscopic metal oxide” means a metal oxide that has a capability of absorbing moisture and chemically reacts with moisture that has been absorbed to become a hydroxide. Specifically, it is one kind selected from calcium oxide, magnesium oxide, strontium oxide, aluminum oxide, barium oxide and the like, or a mixture or solid solution of two or more kinds. Specific examples of the mixture or solid solution of two or more kinds include calcined dolomite (a mixture containing calcium oxide and magnesium oxide), calcined hydrotalcite (solid solution of calcium oxide and aluminum oxide), and the like. It is done.
  • calcium oxide, magnesium oxide, and calcined hydrotalcite are preferable from the viewpoint of high hygroscopicity, cost, and stability of raw materials, and calcined hydrotalcite is more preferable.
  • the calcined hydrotalcite reduces the amount of OH in the chemical structure by calcining natural hydrotalcite (Mg 6 Al 2 (OH) 16 CO 3 ⁇ 4H 2 O) and synthetic hydrotalcite (hydrotalcite-like compound) Or disappeared.
  • a calcined hydrotalcite having a BET specific surface area of 65 m 2 / g or more is particularly preferable.
  • the calcined hydrotalcite having a BET specific surface area of 65 m 2 / g or more preferably has a BET specific surface area of 80 m 2 / g or more, and more preferably 100 m 2 / g or more. Further, BET specific surface area is preferably from 200m 2 / g, more preferably at most 150m 2 / g.
  • the hygroscopic metal oxide is known as a hygroscopic material in various technical fields, and a commercially available product can be used. Specifically, calcium oxide (“Moystop # 10” manufactured by Sankyo Flour Milling Co., Ltd.), magnesium oxide (“Kyowa Mag MF-150”, “Kyowa Mag MF-30” manufactured by Kyowa Chemical Industry Co., Ltd., “Pure Mag” manufactured by Tateho Chemical Industry Co., Ltd. FNMG ”, etc.), lightly burned magnesium oxide (“ TATEHOMAG # 500 ”,“ TATEHOMAG # 1000 ”, TATEHOMAG # 5000”, etc.
  • a surface treated with a surface treatment agent can be used.
  • the surface treatment agent used for the surface treatment for example, higher fatty acids, alkylsilanes, silane coupling agents and the like can be used, and among these, higher fatty acids and alkylsilanes are preferable.
  • One or more surface treatment agents can be used.
  • higher fatty acid examples include higher fatty acids having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid, and palmitic acid, among which stearic acid is preferable. You may use these 1 type or in combination of 2 or more types.
  • Alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl ( And 3- (trimethoxysilyl) propyl) ammonium chloride. You may use these 1 type or in combination of 2 or more types.
  • silane coupling agent examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy.
  • Epoxy silane coupling agents such as silane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane ; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltri Amino-based silane cups such as toxisilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Ringing agents; Ureido silane coupling agents such
  • the surface treatment of the hygroscopic metal oxide is performed, for example, by adding and spraying the surface treatment agent and stirring for 5 to 60 minutes while stirring and dispersing the untreated hygroscopic metal oxide at room temperature with a mixer.
  • a mixer a well-known mixer can be used, for example, blenders, such as V blender, a ribbon blender, and a bubble cone blender, mixers, such as a Henschel mixer and a concrete mixer, a ball mill, a cutter mill, etc. are mentioned.
  • the hygroscopic material is pulverized with a ball mill or the like
  • a method of surface treatment by mixing the above-mentioned higher fatty acid, alkylsilanes or silane coupling agent is also possible.
  • the treatment amount of the surface treatment agent varies depending on the type of the hygroscopic metal oxide or the type of the surface treatment agent, but is preferably 1 to 10% by mass with respect to the hygroscopic metal oxide.
  • Hygroscopic metal oxides may be used alone or in combination of two or more.
  • the resin composition of the present invention contains a hygroscopic metal compound
  • its content is not particularly limited, but from the viewpoint of preventing the strength of the cured product from being reduced and becoming brittle, the resin composition 50 mass% or less is preferable with respect to 100 mass% of non volatile matters in it, 40 mass% or less is more preferable, and 30 mass% or less is still more preferable.
  • the content is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass with respect to 100% by mass of the nonvolatile content in the resin composition. % Or more is more preferable.
  • the resin composition of the present invention can improve the flexibility and moldability of the resin composition by further containing a plasticizer.
  • a plasticizer A liquid material is suitably used at room temperature.
  • plasticizers include paraffinic process oil, naphthenic process oil, liquid paraffin, polyethylene wax, polypropylene wax, petroleum jelly and other mineral oils, castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, palm oil, olive oil. And other liquid oils such as vegetable oil, liquid polybutene, hydrogenated liquid polybutene, liquid polybutadiene, and hydrogenated liquid polybutadiene.
  • liquid poly ⁇ -olefins are preferable, and liquid polybutadiene is particularly preferable.
  • the liquid poly ⁇ -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 5000, more preferably 1000 to 3000.
  • plasticizers may be used alone or in combination of two or more.
  • “liquid” means a state of a plasticizer at room temperature (25 ° C.).
  • the resin composition of the present invention contains a plasticizer, when the nonvolatile content in the resin composition is 100% by mass, from the viewpoint of not having an adverse effect on the organic EL element, within the range of 50% by mass or less. used.
  • the resin composition of the present invention may optionally contain various additives other than the above-described components to the extent that the effects of the present invention are not impaired.
  • additives include silica, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, and strontium titanate.
  • Inorganic fillers such as calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate; organic fillers such as rubber particles, silicone powder, nylon powder, fluororesin powder; Orben, Benton Thickeners such as silicon-based, fluorine-based, polymer-based antifoaming agents or leveling agents; adhesion imparting agents such as triazole compounds, thiazole compounds, triazine compounds, porphyrin compounds; and the like.
  • the method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the compounding ingredients are mixed with a kneading roller, a rotary mixer, or the like, if necessary, by adding a solvent or the like.
  • the resin composition of the present invention is used for sealing electronic parts such as semiconductors, solar cells, high-brightness LEDs, LCDs and EL elements.
  • it is preferably used for sealing an organic EL element, and specifically, applied to the upper part and / or the periphery (side part) of the light emitting part of the organic EL element to protect the light emitting part of the organic EL element from the outside. Can be used.
  • the transparency of the sealing layer formed of the resin composition can be measured with a spectrophotometer.
  • the parallel line transmittance at 450 nm is preferably 80% or more, more preferably 82% or more, still more preferably 84% or more, and still more preferably 86% or more, 88% or more is particularly preferable, and 90% or more is particularly preferable.
  • the resin composition of the present invention comprises (A) an ester bond formed by reacting an acid anhydride group of a polyolefin resin modified with (meth) acrylic acid alkyl ester and an acid anhydride and an epoxy group of (B) an epoxy resin. Is preferably formed.
  • a sealing layer excellent in adhesion moisture heat resistance, moisture permeability resistance, and the like can be formed.
  • an organic solvent is contained in the resin composition, a varnish-like resin composition is prepared, and the varnish is heated and dried. The organic solvent can be dried by blowing hot air or the like.
  • organic solvents examples include ketones such as acetone, methyl ethyl ketone (hereinafter also abbreviated as “MEK”), cyclohexanone; and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate.
  • ketones such as acetone, methyl ethyl ketone (hereinafter also abbreviated as “MEK”), cyclohexanone
  • acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate.
  • Carbitols such as cellosolve and butyl carbitol
  • aromatic hydrocarbons such as toluene and xylene
  • dimethylformamide dimethylacetamide, N-methylpyrrolidone
  • aromatic mixed solvents examples include “Swazole” (trade name, manufactured by Maruzen Petroleum Corporation) and “Ipsol” (trade name, manufactured by Idemitsu Kosan Co., Ltd.). You may use an organic solvent 1 type or in combination of 2 or more types.
  • Drying conditions are not particularly limited, but preferably 50 to 100 ° C. for 1 to 60 minutes. By setting it as 50 degreeC or more, it becomes easy to reduce the amount of solvent which remains in a resin composition layer.
  • the sealing sheet of the present invention is a sealing sheet in which an adhesive layer is formed on a support, and the adhesive layer is formed of the resin composition of the present invention.
  • the adhesive layer is formed, for example, by preparing a varnish obtained by dissolving the resin composition of the present invention in an organic solvent, and applying and drying the varnish on a support.
  • the organic solvent can be dried by blowing hot air or the like. During this drying, an ester bond formed by the reaction of the acid anhydride group of the component (A) and the epoxy group of the component (B) in the resin composition is formed. It is preferable.
  • the resin composition becomes a pressure-sensitive adhesive resin composition excellent in adhesion moisture heat resistance, moisture permeation resistance, and the like.
  • the organic solvent include those similar to the organic solvent, and the drying conditions can be the same as the drying conditions.
  • the thickness of the adhesive layer in the sealing sheet is preferably 3 ⁇ m to 200 ⁇ m, more preferably 5 ⁇ m to 100 ⁇ m, and even more preferably 5 ⁇ m to 50 ⁇ m.
  • the final sealing structure of interest is a structure in which a sealing substrate is laminated on an adhesive layer (resin composition layer)
  • the portion where moisture can enter is on the side of the adhesive layer. Therefore, by reducing the thickness of the adhesive layer, the area in contact with the outside air on the side portion is reduced. Therefore, it is desirable to reduce the thickness of the adhesive layer in order to block moisture.
  • the layer thickness of the adhesive layer is too small, the element may be damaged when the sealing substrate is bonded, and the workability when the sealing substrate is bonded tends to be lowered.
  • setting the thickness of the adhesive layer within the above preferable range means that the uniformity of the thickness of the adhesive layer after the adhesive layer is transferred to a sealing target (for example, a substrate on which an element such as an organic EL element is formed). It is also effective in maintaining.
  • a support having moisture resistance is preferable.
  • the moisture-proof support include a moisture-proof plastic film, a metal foil such as a copper foil and an aluminum foil, and the like.
  • the plastic film having moisture resistance include a plastic film in which an inorganic substance such as silicon oxide (silica), silicon nitride, SiCN, amorphous silicon or the like is deposited on the surface.
  • examples of the plastic film on which an inorganic substance is deposited on the surface include, for example, polyolefin (for example, polyethylene, polypropylene, polyvinyl chloride, etc.), polyester (for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”). , Polyethylene naphthalate, etc.), plastic films such as polycarbonate and polyimide are preferred, and PET films are particularly preferred.
  • examples of commercially available moisture-proof plastic films include the Tech Barrier HX, AX, LX, L series (Mitsubishi Resin Co., Ltd.) and the moisture barrier effect even more than the Tech Barrier HX, AX, LX, L series. X-BARRIER (manufactured by Mitsubishi Plastics), etc.
  • the support having moisture resistance a support having a multilayer structure of two or more layers, for example, a laminate of the above plastic film and the above metal foil with an adhesive may be used. This is inexpensive and advantageous from the viewpoint of handling properties.
  • the support body which does not have moisture resistance (For example, the single body of the plastic film in which the inorganic substance is not vapor-deposited on the said surface) can also be used for the support body of a resin composition sheet.
  • the thickness of the support is not particularly limited, but is preferably from 10 to 150 ⁇ m, more preferably from 20 to 100 ⁇ m, from the viewpoint of the handleability of the sealing sheet.
  • the surface of the adhesive layer of the present invention has a surface to prevent dust from adhering to the surface of the adhesive layer (resin composition layer) and scratches until it is actually used for forming a sealing structure.
  • the protective film is preferably protected, and as the protective film, the plastic film exemplified in the above support can be used.
  • the protective film may be subjected to a mold release treatment in addition to a mat treatment and a corona treatment.
  • Specific examples of the release agent include a fluorine-based release agent, a silicone-based release agent, and an alkyd resin-based release agent. Different types of release agents may be mixed and used.
  • the thickness of the protective film is not particularly limited, but is preferably 1 to 40 ⁇ m, and more preferably 10 to 30 ⁇ m.
  • the sealing sheet of the present invention is used by being laminated on a sealing target.
  • laminate refers to an adhesive layer (resin composition layer) in which the object to be sealed is covered with a sealing sheet with a support, and the object to be sealed is transferred from the sheet for sealing. ) Covered.
  • a sealing sheet that is a support that does not have moisture resistance for example, a single plastic film with no inorganic material deposited on the surface
  • the sealing sheet is laminated to the object to be sealed. After that, it is preferable to peel the support (that is, transfer the adhesive layer (resin composition layer)), and then separately laminate a sealing substrate on the adhesive layer.
  • the sealing target is a substrate on which an organic EL element is formed (hereinafter, also referred to as “organic EL element forming substrate”)
  • organic EL element forming substrate a mode in which such sealing substrates are laminated.
  • the “sealing substrate” as used in the present invention is the one that uses the moisture-proof support used for the sealing sheet alone without forming an adhesive layer (resin composition layer) on it. It is.
  • a “sealing substrate” also includes a highly moisture-proof plate that does not have flexibility such as a glass plate, a metal plate, and a steel plate, which is unsuitable for use as a support for a sealing sheet.
  • the organic EL device of the present invention is an organic EL device in which an organic EL element is sealed with a sealing layer, and the sealing layer is formed of the resin composition of the present application.
  • the organic EL device of the present invention can be obtained by laminating the sealing sheet of the present invention on a substrate having an organic EL element. When the sealing sheet is protected by a protective film, the organic EL element is removed from the sealing sheet so that the adhesive layer (resin composition layer) is in direct contact with the substrate having the organic EL element. Is laminated on a substrate having The laminating method may be a batch method or a continuous method using a roll.
  • thermosetting is performed. By carrying out like this, the organic EL device by which the organic EL element was sealed with the sealing layer formed with the resin composition of this invention is obtained.
  • a sealing material for an organic EL element needs to be dried before sealing work to remove the absorbed water, and the work is complicated, but the support has moisture resistance. Since the sealing sheet of the present invention using a high moisture permeation resistance, the water absorption rate during storage and device manufacturing operations is also low. Moreover, the damage given to the organic EL element at the time of sealing work is also remarkably reduced.
  • the support sheet When a sealing sheet using a support that does not have moisture resistance is used, the support sheet is peeled off after laminating the sealing sheet on a substrate having an organic EL element, and an exposed adhesive layer (resin composition layer) The sealing process of the organic EL element is completed by pressure-bonding the sealing substrate to the substrate.
  • Two or more sealing substrates may be used by bonding them from the viewpoint of improving the moisture-proof effect.
  • the thickness of the sealing substrate is preferably 5 mm or less, more preferably 1 mm or less, and further preferably 100 ⁇ m or less from the viewpoint of making the organic EL device itself thin and light.
  • the pressure at the time of press-bonding the sealing substrate is preferably about 0.3 to 10 kgf / cm 2 , and 25 to 130 ° C. is preferable when the pressure is applied under heating.
  • the substrate having an organic EL element is an organic EL element formed on a transparent substrate
  • the transparent substrate side is a display surface of a display or a light emitting surface of a lighting fixture
  • a metal plate, metal foil, opaque plastic film, or plate may be used.
  • the sealing substrate side is used as the display surface of the display or the light emitting surface of the lighting fixture. Therefore, a transparent plastic film, a glass plate, a transparent plastic plate or the like is used as the sealing substrate.
  • T-YP429 Modified polyolefin-based resin
  • the maleic anhydride group concentration 0.46 mmol / g, the number average molecular weight 2300 of the modified copolymer, the number average molecular weight 386 of the graft chain, the content of 2-ethylhexyl acrylate units in the graft chain of 50% by mass
  • T-YP430 manufactured by Seiko PMC
  • 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer (ethylene unit / methyl methacrylate unit 68% by mass / 32% by mass, maleic an
  • B epoxy resin 828EL (manufactured by Mitsubishi Chemical Corporation) ): Bisphenol A type epoxy resin, epoxy equivalent 190 g / eq EPICLON EXA4850-1000 (manufact
  • the PET film was peeled off, and a glass plate (length 76 mm, width 26 mm, thickness 1.2 mm, micro slide glass) was further laminated on the exposed resin composition layer under the same conditions as described above.
  • pulling speed 50mm / min was measured (initial adhesive strength).
  • adhesive strength was measured by said method (adhesion strength after a high temperature, high humidity environment test).
  • a sealing sheet was obtained by the method described below. Unless otherwise specified, the value of each part is a value converted in terms of nonvolatile content.
  • Example 1 To 37 parts of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer (T-YP429, 20% toluene solution), purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) 35 parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 27 parts of a glycidyl methacrylate-modified ethylene-methacrylate copolymer (T-YP431, 20% toluene solution) and 0.5 part of an anionic polymerization accelerator (TAP) are uniformly mixed with a high-speed rotating mixer.
  • T-YP429 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer
  • T-YP431 purified cyclohexane ring-containing saturated hydrocarbon resin
  • the obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 ⁇ m) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes.
  • a sealing sheet having a composition layer thickness of 20 ⁇ m was obtained.
  • Example 2 To 37 parts of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer (T-YP430, 20% toluene solution), purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) 35 parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 27 parts of a glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (T-YP432, 20% toluene solution) and 0.5 part of an anionic polymerization accelerator (TAP) are uniformly mixed with a high-speed rotating mixer.
  • T-YP430 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer
  • T-YP432 purified cyclohexane ring-containing saturated hydrocarbon resin
  • the obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 ⁇ m) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes.
  • a sealing sheet having a composition layer thickness of 20 ⁇ m was obtained.
  • Example 3 30 parts of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer (T-YP429, 20% swazole solution), purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) 35 parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 34 parts of an ethylene-glycidyl methacrylate copolymer (BONDAST BF-7M, 20% swazole solution) and 0.5 part of an anionic polymerization accelerator (TAP) were uniformly mixed with a high-speed rotary mixer. A varnish was obtained.
  • T-YP429 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer
  • T-YP429 purified cyclohexane ring-containing saturated hydrocarbon resin
  • TEP anionic
  • the obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 ⁇ m) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes.
  • a sealing sheet having a composition layer thickness of 20 ⁇ m was obtained.
  • Example 4 Mixture of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-propylene copolymer and 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP953, 30% methylcyclohexane + butyl acetate solution) 37 36 parts of a cyclohexane ring-containing saturated hydrocarbon resin purified product (TFS13-030, 60% toluene solution) was mixed with a high-speed rotary mixer to obtain a uniform mixed solution.
  • T-YP953, 30% methylcyclohexane + butyl acetate solution 37 36 parts of a cyclohexane ring-containing saturated hydrocarbon resin purified product (TFS13-030, 60% toluene solution) was mixed with a high-speed rotary mixer to obtain a uniform mixed solution.
  • Example 5 Mixture of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-propylene copolymer and 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP955, 30% methylcyclohexane + butyl acetate solution) 25 36 parts of a cyclohexane ring-containing saturated hydrocarbon resin purified product (TFS13-030, 60% toluene solution) was mixed with a high-speed rotary mixer to obtain a uniform mixed solution.
  • T-YP955 30% methylcyclohexane + butyl acetate solution
  • Example 6 To 16 parts of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-propylene-butene random copolymer (T-YP956, 50% methylcyclohexane + butyl acetate solution) purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030) , 60% toluene solution) was mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution.
  • T-YP956 50% methylcyclohexane + butyl acetate solution
  • T-YP956 50% methylcyclohexane + butyl acetate solution
  • Example 7 50 parts of 2-ethylhexyl acrylate and maleic anhydride-modified propylene-butene copolymer (T-YP279, 40% swazole solution) and 50% purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) The parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution.
  • Example 8 50 parts of cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) is added to 35 parts of 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP279, 40% swazole solution). The parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 2 parts of bisphenol A type epoxy resin (828EL) and 0.5 part of an anionic polymerization accelerator (TAP) were uniformly mixed with a high-speed rotary mixer to obtain a varnish.
  • T-YP279 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer
  • the obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 ⁇ m) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes.
  • a sealing sheet having a composition layer thickness of 20 ⁇ m was obtained.
  • Example 9 50 parts of cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) is added to 35 parts of 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP279, 40% swazole solution). The parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 2 parts of an epoxy resin containing polypropylene glycol skeleton (EPICLON EXA4850-1000) and 0.5 part of an anionic polymerization accelerator (TAP) were uniformly mixed with a high-speed rotary mixer to obtain a varnish.
  • T-YP279 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer
  • the obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 ⁇ m) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes.
  • a sealing sheet having a composition layer thickness of 20 ⁇ m was obtained.
  • Example 10 20 parts of 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP279, 40% swazole solution) and 14 parts of calcined hydrotalcite were mixed and kneaded with three rolls, and then cyclohexane ring-containing saturated 50 parts of purified hydrocarbon resin (TFS13-030, 60% toluene solution) was mixed with a high-speed rotary mixer to obtain a uniform mixed solution.
  • T-YP279 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer
  • 14 parts of calcined hydrotalcite 14 parts of calcined hydrotalcite was mixed and kneaded with three rolls, and then cyclohexane ring-containing saturated 50 parts of purified hydrocarbon resin (TFS13-030, 60% toluene solution) was mixed with a high-speed rotary mixer to obtain a
  • Example 11 28 parts of 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP312, 40% swazole solution) and purified hydrocarbon resin containing cyclohexane ring (TFS13-030, 60% toluene solution) 50 parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 21 parts of a glycidyl methacrylate-modified propylene-butene copolymer (T-YP313, 40% swazole solution) and 0.5 part of an anionic polymerization accelerator (TAP) were uniformly mixed with a high-speed rotary mixer.
  • T-YP312 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer
  • T-YP313 purified hydrocarbon resin containing cyclohexane ring
  • TEP anionic polymer
  • the obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 ⁇ m) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes.
  • a sealing sheet having a composition layer thickness of 20 ⁇ m was obtained.
  • ⁇ Comparative Example 1> Mix 50 parts polypropylene resin (L-MODU S400, 45% swazole solution) and 50 parts purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution), and mix evenly with a high-speed rotary mixer. A solution was obtained. To this mixed solution, 0.5 part of an anionic polymerization accelerator (TAP) was uniformly mixed with a high-speed rotary mixer to obtain a varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 ⁇ m) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 ⁇ m was obtained.
  • TEP anionic polymerization accelerator
  • ⁇ Comparative example 2> Mix 50 parts of styrene-isobutylene-styrene block copolymer (SIBSTAR-102T, 45% swazole solution) and 50 parts of purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution). To obtain a homogeneous mixed solution. To this mixed solution, 0.5 part of an anionic polymerization accelerator (TAP) was uniformly mixed with a high-speed rotary mixer to obtain a varnish.
  • SIBSTAR-102T 45% swazole solution
  • TEP anionic polymerization accelerator
  • the obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 ⁇ m) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes.
  • a resin composition sheet having a composition layer thickness of 20 ⁇ m was obtained.
  • TAP anionic polymerization accelerator
  • Table 1 shows the evaluation results of Examples and Comparative Examples.
  • the encapsulating resin composition of the present invention has good adhesive moist heat resistance and moisture permeability resistance. Also, the processability was good and stable coating was possible.
  • the resin composition of the present invention has both good adhesiveness and adhesive wet heat resistance, and is suitably used for sealing electronic parts such as semiconductors, solar cells, high-brightness LEDs, LCDs, EL elements, etc., and particularly organic EL elements. It is suitably used for sealing.

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Abstract

To provide: a resin composition for sealing, which has excellent adhesiveness, wet heat resistance of adhesion and workability; and a resin composition sheet for sealing, which is obtained from this resin composition for sealing. A resin composition for sealing, which is characterized by containing (A) a polyolefin resin which is modified by an alkyl (meth)acrylate ester and an acid anhydride, (B) an epoxy resin and (C) a tackifying resin.

Description

封止用樹脂組成物Resin composition for sealing
　本発明は、封止用樹脂組成物及び封止用シート等に関し、特に有機ＥＬ素子の封止等に好適に使用できる、封止用樹脂組成物及び封止用シート等に関する。 The present invention relates to an encapsulating resin composition, an encapsulating sheet, and the like, and more particularly to an encapsulating resin composition and an encapsulating sheet that can be suitably used for encapsulating an organic EL element.
　有機ＥＬ（Electroluminescence）素子は発光材料に有機物質を使用した発光素子であり、低電圧で高輝度の発光を得ることができる近年脚光を浴びている素材である。しかしながら、有機ＥＬ素子は水分に極めて弱く、有機材料自体が水分によって変質して、輝度が低下したり、発光しなくなったり、電極と有機ＥＬ層との界面が水分の影響で剥離したり、電極の金属が酸化して高抵抗化してしまう問題があることから、有機ＥＬ素子を封止することが行われている。 An organic EL (Electroluminescence) element is a light-emitting element using an organic substance as a light-emitting material, and has been attracting attention in recent years because it can emit light with high luminance at a low voltage. However, the organic EL element is extremely vulnerable to moisture, and the organic material itself is altered by moisture, resulting in a decrease in brightness, no light emission, or the interface between the electrode and the organic EL layer being peeled off due to moisture, Since there is a problem that the metal is oxidized to increase the resistance, the organic EL element is sealed.
　熱硬化樹脂組成物を、有機ＥＬ素子を有する基板の全面封止材料として使用する場合、硬化前の材料粘度が低いことから積層作業が容易であることや、熱硬化後の硬化物の耐透湿性が高いことが利点として挙げられる。しかし、その一方で、熱硬化時の加熱温度によって有機ＥＬ素子が劣化するという問題がある。 When the thermosetting resin composition is used as a sealing material for the entire surface of a substrate having an organic EL element, the laminating work is easy because the material viscosity before curing is low, and the permeation resistance of the cured product after thermosetting is low. An advantage is high wetness. However, on the other hand, there is a problem that the organic EL element deteriorates due to the heating temperature during thermosetting.
　有機ＥＬ素子の熱劣化を回避する方法としては感圧接着剤を封止材料として用いる方法が挙げられる。例えば、特許文献１には、ポリイソブチレン樹脂、エポキシ基と反応し得る官能基を持つポリイソプレン樹脂および／またはポリイソブチレン樹脂、粘着付与樹脂、並びにエポキシ樹脂を含有する樹脂組成物にて封止する技術が開示されている。また、特許文献２には、スチレン－イソブチレン変性樹脂および粘着付与樹脂を含有する樹脂組成物にて封止する技術が開示されている。 As a method for avoiding thermal degradation of the organic EL element, a method using a pressure sensitive adhesive as a sealing material can be mentioned. For example, Patent Document 1 discloses sealing with a polyisobutylene resin, a polyisoprene resin having a functional group capable of reacting with an epoxy group and / or a polyisobutylene resin, a tackifying resin, and a resin composition containing an epoxy resin. Technology is disclosed. Patent Document 2 discloses a technique of sealing with a resin composition containing a styrene-isobutylene-modified resin and a tackifier resin.
国際公開2011/062167号パンフレットInternational publication 2011/062167 pamphlet 国際公開2013/108731号パンフレットInternational publication 2013/108731 pamphlet
　支持体上に感圧接着剤層を形成して封止用シートとする場合、熱硬化樹脂組成物を使用する場合と比較し、耐透湿性がより重要な課題となる。特に有機ＥＬ素子等の封止用途にはより高度な耐透湿性が要求される。また封止後の吸湿による感圧接着剤の基板との接着強度低下も課題となり、接着湿熱耐性の改善も望まれていた。よって本発明が解決しようとする課題は、接着湿熱耐性および耐透湿性に優れた封止用樹脂組成物を提供することにある。 When a pressure-sensitive adhesive layer is formed on a support to form a sealing sheet, moisture resistance is a more important issue than when a thermosetting resin composition is used. In particular, a higher degree of moisture permeability is required for sealing applications such as organic EL elements. In addition, a decrease in the adhesive strength of the pressure-sensitive adhesive to the substrate due to moisture absorption after sealing has been an issue, and improvement in the resistance to heat and moisture of adhesion has been desired. Therefore, the problem to be solved by the present invention is to provide a sealing resin composition excellent in adhesion wet heat resistance and moisture permeability resistance.
　本発明者は上記課題の解決のために鋭意検討した結果、（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂、（Ｂ）エポキシ樹脂および（Ｃ）粘着付与樹脂を含有することを特徴とする封止用樹脂組成物が、封止前の加熱により良好な架橋構造が形成され、接着湿熱耐性、耐透湿性に優れる感圧接着性の組成物となることを見出し、本発明を完成するに至った。 As a result of diligent studies for solving the above-mentioned problems, the present inventor has (A) (meth) acrylic acid alkyl ester and polyolefin-based resin modified with acid anhydride, (B) epoxy resin, and (C) tackifying resin. A sealing resin composition characterized by containing a pressure-sensitive adhesive composition having a good cross-linking structure formed by heating before sealing, and having excellent resistance to moisture and heat resistance and moisture permeability. The headline and the present invention were completed.
　すなわち本発明は以下の態様を含む。
［１］　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂、（Ｂ）エポキシ樹脂、並びに（Ｃ）粘着付与樹脂を含有することを特徴とする封止用樹脂組成物。
［２］　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂が、ポリオレフィン系樹脂の主鎖に（メタ）アクリル酸アルキルエステル単位及び酸無水物単位を含むグラフトポリマーが結合したグラフト変性体であり、該グラフトポリマーの数平均分子量が１００以上である、上記［１］に記載の封止用樹脂組成物。
［３］　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂における、（メタ）アクリル酸アルキルエステルのアルキル基の炭素原子数が１～１８である、上記［１］または［２］に記載の封止用樹脂組成物。
［４］　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂における酸無水物基の濃度が０．０５～１０ｍｍｏｌ／ｇである、上記［１］～［３］のいずれか１つに記載の封止用樹脂組成物。
［５］　（Ｂ）エポキシ樹脂が、エポキシ変性ポリオレフィン系樹脂である、上記［１］～［４］のいずれか１つに記載の封止用樹脂組成物。
［６］　エポキシ変性ポリオレフィン系樹脂におけるエポキシ基濃度が０．０５～１０ｍｍｏｌ／ｇである、上記［５］に記載の封止用樹脂組成物。
［７］　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂および（Ｂ）エポキシ樹脂の合計の含有量が、樹脂組成物中の不揮発分を１００質量％とした場合、５～８０質量％である、上記［１］～［６］のいずれか１つに記載の封止用樹脂組成物。
［８］　（Ｃ）粘着付与樹脂の含有量が、樹脂組成物中の不揮発分を１００質量％とした場合、５～８０質量％である、上記［１］～［７］のいずれか１つに記載の封止用樹脂組成物。
［９］　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂の酸無水物基と（Ｂ）エポキシ樹脂のエポキシ基が反応して生じるエステル結合が形成されている、上記［１］～［８］のいずれか１つに記載の封止用樹脂組成物。
［１０］　有機ＥＬ素子の封止用である、上記［１］～［９］のいずれか１つに記載の封止用樹脂組成物。
［１１］　支持体上に接着層が形成された封止用シートであって、該接着層が、上記［１］～［９］のいずれか１つに記載の封止用樹脂組成物により形成されている、封止用シート。
［１２］　有機ＥＬ素子の封止用である上記［１１］記載の封止用シート。
［１３］　有機ＥＬ素子が封止層により封止されている有機ＥＬデバイスであって、該封止層が、上記［１］～［１０］のいずれか１つに記載の封止用樹脂組成物により形成されている、有機ＥＬデバイス。
［１４］　有機ＥＬ素子が封止層により封止されている有機ＥＬデバイスであって、該封止層が、上記［１１］または［１２］に記載の封止用シートの接着層により形成されている、有機ＥＬデバイス。
［１５］　上記［１］～［９］のいずれか１つに記載の封止用樹脂組成物を含む樹脂ワニスを、支持体上に塗布および加熱乾燥し、（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂の酸無水物基と（Ｂ）エポキシ樹脂のエポキシ基とが反応によりエステル結合した接着層を形成することを特徴とする、封止用シートの製造方法。 That is, the present invention includes the following aspects.
[1] A sealing resin comprising (A) a (meth) acrylic acid alkyl ester and a polyolefin-based resin modified with an acid anhydride, (B) an epoxy resin, and (C) a tackifying resin. Composition.
[2] Graft polymer wherein (A) polyolefin resin modified with (meth) acrylic acid alkyl ester and acid anhydride contains (meth) acrylic acid alkyl ester unit and acid anhydride unit in the main chain of polyolefin resin The encapsulating resin composition according to the above [1], wherein is a graft-modified product in which is bonded, and the number average molecular weight of the graft polymer is 100 or more.
[3] (A) In the polyolefin resin modified with (meth) acrylic acid alkyl ester and acid anhydride, the alkyl group of (meth) acrylic acid alkyl ester has 1 to 18 carbon atoms, [1] ] Or the sealing resin composition according to [2].
[4] The above [1] to [3], wherein the concentration of the acid anhydride group in the polyolefin resin modified with (A) (meth) acrylic acid alkyl ester and acid anhydride is 0.05 to 10 mmol / g. The resin composition for sealing as described in any one of these.
[5] The sealing resin composition according to any one of [1] to [4] above, wherein the (B) epoxy resin is an epoxy-modified polyolefin resin.
[6] The encapsulating resin composition according to [5], wherein the epoxy group concentration in the epoxy-modified polyolefin resin is 0.05 to 10 mmol / g.
[7] (A) The total content of (A) (meth) acrylic acid alkyl ester and an acid anhydride-modified polyolefin resin and (B) epoxy resin is 100% by mass of the nonvolatile content in the resin composition. In this case, the encapsulating resin composition according to any one of [1] to [6] above, which is 5 to 80% by mass.
[8] Any one of the above [1] to [7], wherein the content of the (C) tackifying resin is 5 to 80% by mass when the nonvolatile content in the resin composition is 100% by mass. 2. The sealing resin composition according to 1.
[9] (A) An ester bond formed by reacting an acid anhydride group of a polyolefin resin modified with (meth) acrylic acid alkyl ester and acid anhydride and an epoxy group of (B) epoxy resin is formed. The sealing resin composition according to any one of [1] to [8] above.
[10] The sealing resin composition according to any one of [1] to [9], which is used for sealing an organic EL element.
[11] A sealing sheet having an adhesive layer formed on a support, wherein the adhesive layer is formed of the sealing resin composition according to any one of [1] to [9]. A sealing sheet.
[12] The sealing sheet according to [11], which is used for sealing an organic EL element.
[13] An organic EL device in which the organic EL element is sealed with a sealing layer, wherein the sealing layer is the sealing resin composition according to any one of the above [1] to [10] An organic EL device that is formed of a material.
[14] An organic EL device in which an organic EL element is sealed with a sealing layer, and the sealing layer is formed by the adhesive layer of the sealing sheet according to [11] or [12]. An organic EL device.
[15] A resin varnish containing the sealing resin composition according to any one of the above [1] to [9] is applied onto a support and heat-dried, and (A) an alkyl (meth) acrylate Production of a sealing sheet, wherein an acid anhydride group of a polyolefin-based resin modified with an ester and an acid anhydride and an epoxy group of (B) an epoxy resin are ester-bonded by reaction to form an adhesive layer Method.
　本発明によれば、接着湿熱耐性および耐透湿性に優れた封止用樹脂組成物およびそれから得られる封止用シート、並びに、該封止用樹脂組成物で封止された有機ＥＬデバイスが提供される。 ADVANTAGE OF THE INVENTION According to this invention, the sealing resin composition excellent in the adhesion heat-and-moisture resistance and moisture permeability resistance, the sealing sheet obtained from it, and the organic EL device sealed with this sealing resin composition are provided. Is done.
　以下、本発明を詳細に説明する。
　本発明の封止用樹脂組成物（以下、単に「樹脂組成物」とも略称する）は、（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂、（Ｂ）エポキシ樹脂、並びに（Ｃ）粘着付与樹脂を含有することが主たる特徴である。 Hereinafter, the present invention will be described in detail.
The encapsulating resin composition of the present invention (hereinafter also simply referred to as “resin composition”) is (A) a polyolefin-based resin modified with (meth) acrylic acid alkyl ester and acid anhydride, and (B) epoxy. The main feature is that it contains a resin and (C) a tackifying resin.
＜（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂＞　
　本発明の樹脂組成物には、（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂（以下、「変性ポリオレフィン系樹脂」または「（Ａ）成分」と称することがある。）が使用される。 <(A) Polyolefin resin modified with (meth) acrylic acid alkyl ester and acid anhydride>
The resin composition of the present invention includes a polyolefin resin modified with a (meth) acrylic acid alkyl ester and an acid anhydride (hereinafter sometimes referred to as “modified polyolefin resin” or “(A) component”). Is used.
（ポリオレフィン系樹脂）
　本発明で使用する変性ポリオレフィン系樹脂の主骨格（変性成分を除いた骨格）のポリオレフィン系樹脂としては、オレフィンモノマー由来の骨格を有するものであれば特に限定されない。例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリブテン系樹脂、ポリイソブチレン系樹脂等が挙げられる。なかでも、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリブテン系樹脂が好ましく、ポリエチレン系樹脂、ポリプロピレン系樹脂が特に好ましい。なお、ここでいう、ポリエチレン系樹脂とは、エチレンのホモポリマーか、或いは、主たる単量体単位（５０質量％超の単量体単位）がエチレンからなる、少なくとも、エチレンと、エチレン以外の単量体単位（例えば、エチレンを除くオレフィン、非共役ジエン、（メタ）アクリル酸アルキルエステル等の単量体単位）を含む共重合体を意味し、ポリプロピレン系樹脂とは、プロピレンのホモポリマーか、或いは、主たる単量体単位（５０質量％超の単量体単位）がプロピレンからなる、少なくとも、プロピレンと、プロピレン以外の単量体単位（例えば、プロピレンを除くオレフィン、非共役ジエン、（メタ）アクリル酸アルキルエステル等の単量体単位）を含む共重合体を意味し、ポリブテン系樹脂とは、ブテンのホモポリマーか、或いは、主たる単量体単位（５０質量％超の単量体単位）がブテンからなる、少なくとも、ブテンと、ブテン以外の単量体単位（例えば、ブテンを除くオレフィン、非共役ジエン、（メタ）アクリル酸アルキルエステル等の単量体単位）を含む共重合体を意味し、ポリイソブチレン系樹脂とは、イソブチレンのホモポリマーか、或いは、主たる単量体単位（５０質量％超の単量体単位）がイソブチレンからなる、少なくとも、イソブチレンと、イソブチレン以外の単量体単位（例えば、イソブチレンを除くオレフィン、非共役ジエン、（メタ）アクリル酸アルキルエステル等の単量体単位）を含む共重合体を意味する。
　例えば、加工性の観点、樹脂組成物を封止シートの接着層としたときの接着層の埋め込み性の観点からは、ポリエチレン系樹脂がポリプロピレン系樹脂より優れている。ここで「加工性」とは、特に変性ポリオレフィン系樹脂をフィルム（層）に形成する際の加工性であり、フィルム（層）形成を可能にするための樹脂ワニスの流動性の持続性（経時安定性）等を含む。一方、耐熱性の観点からは、ポリプロピレン系樹脂がポリエチレン系樹脂より優れている。 (Polyolefin resin)
The polyolefin resin of the main skeleton of the modified polyolefin resin used in the present invention (skeleton excluding the modified component) is not particularly limited as long as it has a skeleton derived from an olefin monomer. For example, a polyethylene resin, a polypropylene resin, a polybutene resin, a polyisobutylene resin, and the like can be given. Of these, polyethylene resins, polypropylene resins, and polybutene resins are preferable, and polyethylene resins and polypropylene resins are particularly preferable. The polyethylene-based resin referred to here is a homopolymer of ethylene or a main monomer unit (a monomer unit of more than 50% by mass) made of ethylene. At least ethylene and a unit other than ethylene are used. It means a copolymer containing a monomer unit (for example, a monomer unit such as an olefin excluding ethylene, a non-conjugated diene, an alkyl (meth) acrylate), and the polypropylene resin is a homopolymer of propylene, Alternatively, the main monomer unit (a monomer unit of more than 50% by mass) is composed of propylene, at least propylene and monomer units other than propylene (for example, olefins other than propylene, non-conjugated dienes, (meth) A polybutene-based resin is a homopolymer of butene, or Is a main monomer unit (a monomer unit of more than 50% by mass) consisting of butene, but at least butene and a monomer unit other than butene (for example, olefin excluding butene, non-conjugated diene, (meth) The polyisobutylene resin is a homopolymer of isobutylene or the main monomer unit (a monomer unit of more than 50% by mass). ) Is a copolymer comprising at least isobutylene and a monomer unit other than isobutylene (eg, a monomer unit such as an olefin excluding isobutylene, a non-conjugated diene, or a (meth) acrylic acid alkyl ester). means.
For example, from the viewpoint of workability and from the viewpoint of embedding property of the adhesive layer when the resin composition is used as the adhesive layer of the sealing sheet, the polyethylene resin is superior to the polypropylene resin. Here, “processability” refers to processability particularly when a modified polyolefin resin is formed on a film (layer), and the fluidity of the resin varnish to enable film (layer) formation (time-lapse). Stability) and the like. On the other hand, from the viewpoint of heat resistance, polypropylene resin is superior to polyethylene resin.
　ポリオレフィン系樹脂をより好ましい特性にする等の理由から、ポリオレフィン系樹脂には、ランダム共重合体、ブロック共重合体等の共重合体を使用することが好ましい。共重合体としては、（ｉ）２種以上のオレフィンの共重合体、（ｉｉ）オレフィンと非共役ジエンの共重合体、または（ｉｉｉ）オレフィンとスチレン等のオレフィン以外のモノマー（非共役ジエンを除く）との共重合体が挙げられる。ここで、（ｉｉ）の共重合体及び（ｉｉｉ）の共重合体において、オレフィンは１種または２種以上を使用できる。 For reasons such as making the polyolefin resin more preferable, it is preferable to use a copolymer such as a random copolymer or a block copolymer for the polyolefin resin. The copolymer includes (i) a copolymer of two or more olefins, (ii) a copolymer of olefin and non-conjugated diene, or (iii) a monomer other than olefin such as olefin and styrene (non-conjugated diene). And a copolymer thereof. Here, in the copolymer of (ii) and the copolymer of (iii), the olefin can use 1 type (s) or 2 or more types.
　ポリオレフィン系樹脂における共重合体の具体例としては、例えば、エチレン－非共役ジエン共重合体、エチレン－（メタ）アクリル酸アルキルエステル共重合体、エチレン－ブテン共重合体、エチレン－ブテン－非共役ジエン共重合体、エチレン－ブテン－（メタ）アクリル酸アルキルエステル共重合体、エチレン－プロピレン共重合体、エチレン－プロピレン－非共役ジエン共重合体、エチレン－プロピレン－ブテン共重合体、エチレン－プロピレン－（メタ）アクリル酸アルキルエステル共重合体、プロピレン－非共役ジエン共重合体、プロピレン－（メタ）アクリル酸アルキルエステル共重合体、プロピレン－ブテン共重合体、プロピレン－ブテン－非共役ジエン共重合体、プロピレン－ブテン－（メタ）アクリル酸アルキルエステル共重合体、イソブチレン－非共役ジエン共重合体、イソブチレン－（メタ）アクリル酸アルキルエステル共重合体、イソブチレン－ブテン共重合体、イソブチレン－ブテン－非共役ジエン共重合体、イソブチレン－ブテン－（メタ）アクリル酸アルキルエステル共重合体、スチレン－イソブチレン共重合体、スチレン－イソブチレン－スチレン共重合体等が挙げられる。
なかでも、エチレン－（メタ）アクリル酸アルキルエステル共重合体、エチレン－ブテン共重合体、エチレン－ブテン－（メタ）アクリル酸アルキルエステル共重合体、エチレン－プロピレン共重合体、エチレン－プロピレン－（メタ）アクリル酸アルキルエステル共重合体、エチレン－プロピレン－ブテン共重合体、プロピレン－ブテン共重合体、プロピレン－ブテン－（メタ）アクリル酸アルキルエステル共重合体、イソブチレン－ブテン共重合体、イソブチレン－ブテン－（メタ）アクリル酸アルキルエステル共重合体等が好ましい。 Specific examples of the copolymer in the polyolefin resin include, for example, ethylene-nonconjugated diene copolymer, ethylene- (meth) acrylic acid alkyl ester copolymer, ethylene-butene copolymer, ethylene-butene-nonconjugated. Diene copolymer, ethylene-butene- (meth) acrylic acid alkyl ester copolymer, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-propylene-butene copolymer, ethylene-propylene -(Meth) acrylic acid alkyl ester copolymer, propylene-nonconjugated diene copolymer, propylene- (meth) acrylic acid alkyl ester copolymer, propylene-butene copolymer, propylene-butene-nonconjugated diene copolymer Combined, propylene-butene- (meth) acrylic acid alkyl ester Copolymer, isobutylene-nonconjugated diene copolymer, isobutylene- (meth) acrylic acid alkyl ester copolymer, isobutylene-butene copolymer, isobutylene-butene-nonconjugated diene copolymer, isobutylene-butene- (meta) ) Acrylic acid alkyl ester copolymer, styrene-isobutylene copolymer, styrene-isobutylene-styrene copolymer, and the like.
Among them, ethylene- (meth) acrylic acid alkyl ester copolymer, ethylene-butene copolymer, ethylene-butene- (meth) acrylic acid alkyl ester copolymer, ethylene-propylene copolymer, ethylene-propylene- ( (Meth) acrylic acid alkyl ester copolymer, ethylene-propylene-butene copolymer, propylene-butene copolymer, propylene-butene- (meth) acrylic acid alkyl ester copolymer, isobutylene-butene copolymer, isobutylene- A butene- (meth) acrylic acid alkyl ester copolymer is preferred.
　なお、上記の例示の共重合体は、単量体成分を並記する形式で記載しており、共重合体の形態は特定していない。即ち、いずれの共重合体も、ランダム共重合体であっても、ブロック共重合体であってもよい。また、二元共重合体のブロック共重合体の場合、ブロック共重合体は、ジブロック共重合体であっても、トリブロック共重合体であってもよい。即ち、例えば、エチレン－ブテン共重合体のブロック共重合体は、ポリエチレンブロック（ポリエチレン骨格）－ポリブテンブロック（ポリブテン骨格）からなるジブロック共重合体（ポリエチレンブロックとポリブテンブロックの交互の繰り返しからなるマルチブロック共重合体を含む）、ポリエチレンブロック（ポリエチレン骨格）－ポリブテンブロック（ポリブテン骨格）－ポリエチレンブロック（ポリエチレン骨格）からなるトリブロック共重合体、ポリブテンブロック（ポリブテン骨格）－ポリエチレンブロック（ポリエチレン骨格）－ポリブテンブロック（ポリブテン骨格）からなるトリブロック共重合体を含む。エチレン－ブテン共重合体以外の二元共重合体においても同様である。 It should be noted that the above-described exemplary copolymers are described in a form in which monomer components are listed, and the form of the copolymer is not specified. That is, any copolymer may be a random copolymer or a block copolymer. In the case of a block copolymer of a binary copolymer, the block copolymer may be a diblock copolymer or a triblock copolymer. That is, for example, an ethylene-butene copolymer block copolymer is a diblock copolymer (polyethylene block (polyethylene skeleton) -polybutene block (polybutene skeleton)) consisting of a multi-block consisting of alternating repeating polyethylene blocks and polybutene blocks. Block copolymer), polyethylene block (polyethylene skeleton) -polybutene block (polybutene skeleton) -triblock copolymer consisting of polyethylene block (polyethylene skeleton), polybutene block (polybutene skeleton) -polyethylene block (polyethylene skeleton)- A triblock copolymer comprising a polybutene block (polybutene skeleton) is included. The same applies to binary copolymers other than ethylene-butene copolymers.
　ポリエチレン系樹脂は、例えば、耐熱性等を向上させる観点から、エチレン－プロピレン共重合体、エチレン－ブテン共重合体、エチレン－プロピレン－ブテン共重合体等を使用することができる。また、プロピレン系樹脂は、例えば、加工性、埋め込み性等を向上させる観点から、プロピレン－エチレン共重合体、プロピレン－ブテン共重合体、エチレン－プロピレン－ブテン共重合体を使用することができ、さらに耐熱性を向上させる観点からはプロピレン－ブテン共重合体を使用することができる。 As the polyethylene resin, for example, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-butene copolymer and the like can be used from the viewpoint of improving heat resistance and the like. In addition, as the propylene-based resin, for example, from the viewpoint of improving processability and embedding property, a propylene-ethylene copolymer, a propylene-butene copolymer, and an ethylene-propylene-butene copolymer can be used. Further, from the viewpoint of improving heat resistance, a propylene-butene copolymer can be used.
　本発明で使用するブテンとしては特に限定はなく、１－ブテン、ｃｉｓ－２－ブテン、ｔｒａｎｓ－２－ブテン、イソブテン（別称：２－メチルプロペン）等を挙げることができ、これらは１種または２種以上を組合せて用いることができるが、好ましくは、１－ブテンである。なお、２種以上のブテンが使用される場合、例えば、エチレン－ブテン共重合体においては、エチレンと２種以上のブテンが共重合した共重合体であってもよいし、ブテン単位が互いに異なるブテンからなる２種以上のエチレン－ブテン共重合体の混合物であってもよい。また、エチレン－ブテン共重合体の形態は、特に限定されず、ランダム共重合体であっても、ブロック共重合体であってもよいが、なかでも、加工性を向上させる観点から、ランダム共重合体が好ましい。 The butene used in the present invention is not particularly limited, and can include 1-butene, cis-2-butene, trans-2-butene, isobutene (other name: 2-methylpropene), and the like. Two or more types can be used in combination, but 1-butene is preferred. When two or more types of butene are used, for example, the ethylene-butene copolymer may be a copolymer obtained by copolymerizing ethylene and two or more types of butene, or the butene units are different from each other. It may be a mixture of two or more ethylene-butene copolymers comprising butene. The form of the ethylene-butene copolymer is not particularly limited, and may be a random copolymer or a block copolymer. Among them, from the viewpoint of improving processability, the random copolymer is used. Polymers are preferred.
　ポリオレフィン系樹脂の単量体単位として含まれていてもよい他のオレフィン（すなわち、エチレン、プロピレン、ブテンおよびイソブチレン以外のオレフィン）としては、１－ペンテン、３－メチル－１－ヘキセン、３－メチル－１－ペンテン、４－メチル－１－ペンテン、３－エチル－１－ペンテン、１－セプテン、１－オクテン、1－ノネン、１－デセン、１－ウンデセン等の炭素数が２～１１のα－オレフィン（プロピレンおよび１－ブテンを除く）を挙げることができる。なかでも、１－ヘキセンが好ましい。かかるα－オレフィンは１種または２種以上を組み合わせて用いることができる。 Other olefins that may be included as monomer units of polyolefin resins (that is, olefins other than ethylene, propylene, butene, and isobutylene) include 1-pentene, 3-methyl-1-hexene, 3-methyl Α having 2 to 11 carbon atoms, such as -1-pentene, 4-methyl-1-pentene, 3-ethyl-1-pentene, 1-septene, 1-octene, 1-nonene, 1-decene, 1-undecene, etc. Mention may be made of olefins (excluding propylene and 1-butene). Of these, 1-hexene is preferable. Such α-olefins can be used alone or in combination of two or more.
　また、他のオレフィンとして、メチルヘキサジエン（２－メチル－１，５－ヘキサジエン、３－メチル－２，４－ヘキサジエン等）、１，９－デカジエン、１，１３－テトラデカジエン等の炭素数が１０～１４の非共役ジオレフィン化合物を挙げることができる。なかでも、メチルヘキサジエンが好ましく、２－メチル－１，５－ヘキサジエンが特に好ましい。かかる非共役ジオレフィン化合物は１種または２種以上を組み合わせて用いることができる。 Other olefins having a carbon number such as methylhexadiene (2-methyl-1,5-hexadiene, 3-methyl-2,4-hexadiene, etc.), 1,9-decadiene, 1,13-tetradecadiene, etc. There can be mentioned 10 to 14 non-conjugated diolefin compounds. Of these, methylhexadiene is preferable, and 2-methyl-1,5-hexadiene is particularly preferable. Such non-conjugated diolefin compounds can be used alone or in combination of two or more.
　本発明の変性ポリオレフィン系樹脂における主骨格のポリオレフィン系樹脂としては、オレフィンと（メタ）アクリル酸アルキルエステルの共重合体を使用することができる。ここでいう、「（メタ）アクリル酸アルキルエステル」は、アクリル酸アルキルエステル及びメタクリル酸アルキルエステルを意味する。アクリル酸アルキルエステル及びメタクリル酸アルキルエステルはいずれか一方を使用しても、両方を使用してもよい。また、（メタ）アクリル酸アルキルエステルにおけるアルキル基は、非置換アルキル基であっても、置換アルキル基（例えば、アラルキル基）であってもよいが、非置換アルキル基が好ましく、また、該アルキル基は炭素原子数が１～２０が好ましく、より好ましくは１～１０である。（メタ）アクリル酸アルキルエステルの具体例としては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸エチルヘキシル、アクリル酸イソブチル、アクリル酸ベンジル、アクリル酸フェノキシエチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸エチルヘキシル、メタクリル酸イソブチル、メタクリル酸ベンジル、メタクリル酸フェノキシエチル等が挙げられる。なかでも、メタクリル酸メチルが好ましい。（メタ）アクリル酸アルキルエステルは１種または２種以上を使用することができる。 As the polyolefin resin of the main skeleton in the modified polyolefin resin of the present invention, a copolymer of olefin and (meth) acrylic acid alkyl ester can be used. As used herein, “(meth) acrylic acid alkyl ester” means acrylic acid alkyl ester and methacrylic acid alkyl ester. Either one or both of acrylic acid alkyl ester and methacrylic acid alkyl ester may be used. The alkyl group in the (meth) acrylic acid alkyl ester may be an unsubstituted alkyl group or a substituted alkyl group (for example, an aralkyl group), but an unsubstituted alkyl group is preferred. The group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Specific examples of (meth) acrylic acid alkyl esters include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl hexyl acrylate, isobutyl acrylate, benzyl acrylate, phenoxyethyl acrylate, methyl methacrylate, methacrylic acid Examples include ethyl, butyl methacrylate, ethyl hexyl methacrylate, isobutyl methacrylate, benzyl methacrylate, and phenoxyethyl methacrylate. Of these, methyl methacrylate is preferred. One or more (meth) acrylic acid alkyl esters can be used.
　例えば、本発明の変性ポリオレフィン系樹脂において、エチレン－ブテン共重合体、イソブチレン－ブテン共重合体、プロピレン－ブテン共重合体等の少なくともブテンを単量体単位として含む共重合体は、樹脂組成物の接着性、耐透湿性等の性能のバランスの観点から、例えば、エチレン－ブテン共重合体であれば、エチレン単位の含有量は共重合体全体当たり、２０質量％以上であるのが好ましく、３０質量％以上がより好ましく、４０質量％以上がさらに一層好ましく、５０質量％以上が最も好ましい。また、同理由により、９５質量％以下が好ましく、９０質量％以下がより好ましい。なお、イソブチレン－ブテン共重合体におけるイソブチレン単位の含有量、プロピレン－ブテン共重合体におけるプロピレン単位の含有量等も同様である。 For example, in the modified polyolefin resin of the present invention, a copolymer containing at least butene as a monomer unit, such as an ethylene-butene copolymer, an isobutylene-butene copolymer, and a propylene-butene copolymer, is a resin composition. From the viewpoint of the balance of performance such as adhesion and moisture permeability, for example, in the case of an ethylene-butene copolymer, the content of ethylene units is preferably 20% by mass or more based on the whole copolymer, 30 mass% or more is more preferable, 40 mass% or more is still more preferable, and 50 mass% or more is the most preferable. For the same reason, 95% by mass or less is preferable, and 90% by mass or less is more preferable. The same applies to the content of isobutylene units in the isobutylene-butene copolymer, the content of propylene units in the propylene-butene copolymer, and the like.
　また、本発明の変性ポリオレフィン系樹脂において、エチレン－（メタ）アクリル酸アルキルエステル共重合体、イソブチレン－（メタ）アクリル酸アルキルエステル共重合体、プロピレン－（メタ）アクリル酸アルキルエステル共重合体等の、少なくとも（メタ）アクリル酸アルキルエステルを単量体単位として含む、オレフィンと（メタ）アクリル酸アルキルエステルとの共重合体は、樹脂組成物の接着性、耐透湿性等の性能のバランスの観点から、例えば、エチレン－（メタ）アクリル酸アルキルエステル共重合体であれば、エチレン単位の含有量は、共重合体全体当たり、３０質量％以上が好ましく、４０質量％以上がより好ましく、５０質量％以上がさらに一層好ましい。また、同理由により、９５質量％以下が好ましく、９０質量％以下がより好ましい。なお、イソブチレン－（メタ）アクリル酸アルキルエステル共重合体におけるイソブチレン単位の含有量、プロピレン－（メタ）アクリル酸アルキルエステル共重合体におけるプロピレンの含有量等も同様である In the modified polyolefin resin of the present invention, ethylene- (meth) acrylic acid alkyl ester copolymer, isobutylene- (meth) acrylic acid alkyl ester copolymer, propylene- (meth) acrylic acid alkyl ester copolymer, etc. The copolymer of olefin and (meth) acrylic acid alkyl ester, which contains at least (meth) acrylic acid alkyl ester as a monomer unit, has a balance of performance such as adhesion and moisture resistance of the resin composition. From the viewpoint, for example, in the case of an ethylene- (meth) acrylic acid alkyl ester copolymer, the content of ethylene units is preferably 30% by mass or more, more preferably 40% by mass or more, based on the entire copolymer, 50% The mass% or more is even more preferable. For the same reason, 95% by mass or less is preferable, and 90% by mass or less is more preferable. The same applies to the content of isobutylene units in the isobutylene- (meth) acrylic acid alkyl ester copolymer, the content of propylene in the propylene- (meth) acrylic acid alkyl ester copolymer, and the like.
　また、本発明の変性ポリオレフィン系樹脂において、エチレン－ブテン共重合体、プロピレン－ブテン共重合体、イソブチレン－ブテン共重合体等に、エチレン、プロピレン、イソブチレン及びブテンを除く他のオレフィンがさらに共重合した共重合体が使用される場合、該共重合体中のエチレン単位、プロピレン単位、イソブチレン単位、ブテン単位等の特徴を生かす上では、他のオレフィン単位の割合は、エチレン単位とブテン単位と他のオレフィン単位の総量、プロピレン単位とブテン単位と他のオレフィン単位の総量、或いは、イソブチレン単位とブテン単位と他のオレフィン単位の総量に対して、２０質量％以下が好ましく、１０質量％以下がより好ましく、５質量％以下がとりわけ好ましく、３質量％以下が最も好ましい。 In the modified polyolefin resin of the present invention, ethylene-butene copolymer, propylene-butene copolymer, isobutylene-butene copolymer, etc. are further copolymerized with other olefins other than ethylene, propylene, isobutylene and butene. In order to take advantage of the characteristics of the ethylene unit, propylene unit, isobutylene unit, butene unit, etc. in the copolymer, the ratio of the other olefin units is such that the ethylene unit, butene unit and other The total amount of olefin units, the total amount of propylene units, butene units and other olefin units, or the total amount of isobutylene units, butene units and other olefin units is preferably 20% by mass or less, more preferably 10% by mass or less. Preferably, 5% by mass or less is particularly preferable, and 3% by mass or less is most preferable.
　また、本発明の変性ポリオレフィン系樹脂において、エチレン－（メタ）アクリル酸アルキルエステル共重合体、イソブチレン－（メタ）アクリル酸アルキルエステル共重合体、プロピレン－（メタ）アクリル酸アルキルエステル共重合体等に、エチレン、プロピレン及びイソブチレンを除く他のオレフィンがさらに共重合した共重合体が使用される場合、該共重合体中のエチレン単位、プロピレン単位、イソブチレン単位等の特徴を生かす上では、他のオレフィン単位の割合は、エチレン単位と（メタ）アクリル酸アルキルエステル単位と他のオレフィン単位の総量、プロピレン単位と（メタ）アクリル酸アルキルエステル単位と他のオレフィン単位の総量、或いは、イソブチレン単位と（メタ）アクリル酸アルキルエステルブテン単位と他のオレフィン単位の総量に対して、２０質量％以下が好ましく、１０質量％以下がより好ましく、５質量％以下がとりわけ好ましく、３質量％以下が最も好ましい。 In the modified polyolefin resin of the present invention, ethylene- (meth) acrylic acid alkyl ester copolymer, isobutylene- (meth) acrylic acid alkyl ester copolymer, propylene- (meth) acrylic acid alkyl ester copolymer, etc. In addition, when a copolymer in which other olefins other than ethylene, propylene and isobutylene are further copolymerized is used, in order to take advantage of the characteristics of the ethylene unit, propylene unit, isobutylene unit, etc. in the copolymer, The proportion of olefin units is the total amount of ethylene units, (meth) acrylic acid alkyl ester units and other olefin units, propylene units, (meth) acrylic acid alkyl ester units and other olefin units, or isobutylene units ( (Meth) acrylic acid alkyl ester butene unit The total amount of other olefin units, preferably 20 wt% or less, more preferably 10 wt% or less, especially preferably 5 mass% or less, and most preferably 3 wt% or less.
（変性ポリオレフィン系樹脂）
　本発明における変性ポリオレフィン系樹脂は、接着湿熱耐性、耐湿性等の優れた物性を付与する観点から、ポリオレフィン系樹脂が（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたものである。すなわち、本発明における変性ポリオレフィン系樹脂は、ポリオレフィン系樹脂の主鎖に（メタ）アクリル酸アルキルエステル由来の単位及び酸無水物由来の単位を含むグラフト鎖が結合したグラフト変性体である。ここでいう、（メタ）アクリル酸アルキルエステルは、アクリル酸アルキルエステル又はメタクリル酸アルキルエステルを意味し、各々単独で使用してもよく、アクリル酸アルキルエステルおよびメタクリル酸アルキルエステルを混合して用いてもよい。 (Modified polyolefin resin)
The modified polyolefin resin in the present invention is one in which a polyolefin resin is modified with a (meth) acrylic acid alkyl ester and an acid anhydride from the viewpoint of imparting excellent physical properties such as adhesion moisture heat resistance and moisture resistance. That is, the modified polyolefin resin in the present invention is a graft modified product in which a graft chain containing a unit derived from (meth) acrylic acid alkyl ester and a unit derived from an acid anhydride is bonded to the main chain of the polyolefin resin. The (meth) acrylic acid alkyl ester here means an acrylic acid alkyl ester or a methacrylic acid alkyl ester, and each may be used alone, or a mixture of an acrylic acid alkyl ester and a methacrylic acid alkyl ester. Also good.
　（メタ）アクリル酸アルキルエステルにおけるアルキル基の炭素原子数は好ましくは１～１８、より好ましくは１～１４、さらに好ましくは１～１２、特に好ましくは１～１０、最も好ましくは１～８である。（メタ）アクリル酸アルキルエステルの具体例としては、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－プロピル、アクリル酸ｉ－プロピル、アクリル酸ｎ－ブチル、アクリル酸ｉ－ブチル、アクリル酸２－ブチル、アクリル酸ｔ－ブチル、アクリル酸シクロヘキシル、アクリル酸２－エチルヘキシル、アクリル酸ｎ－オクチル、アクリル酸ｎ－ドデシル、アクリル酸ｎ－オクタデシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－プロピル、メタクリル酸ｉ－プロピル、メタクリル酸ｎ－ブチル、メタクリル酸ｉ－ブチル、メタクリル酸２－ブチル、メタクリル酸ｔ－ブチル、メタクリル酸シクロヘキシル、メタクリル酸２－エチルヘキシル、メタクリル酸ｎ－オクチル、メタクリル酸ｎ－ドデシル、メタクリル酸ｎ－オクタデシル、アクリル酸ベンジル、アクリル酸フェノキシエチル等が挙げられる。なかでも、アクリル酸２－エチルヘキシル、メタクリル酸ｎ－ブチル等が好ましく、より好ましくはアクリル酸２－エチルヘキシルである。（メタ）アクリル酸アルキルエステルは１種または２種以上を使用することができる。 The number of carbon atoms of the alkyl group in the (meth) acrylic acid alkyl ester is preferably 1 to 18, more preferably 1 to 14, still more preferably 1 to 12, particularly preferably 1 to 10, and most preferably 1 to 8. . Specific examples of (meth) acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, and 2-butyl acrylate. , T-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacryl I-propyl acid, n-butyl methacrylate, i-butyl methacrylate, 2-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate , Methacryl n- octadecyl, benzyl acrylate, acrylic acid phenoxyethyl and the like. Of these, 2-ethylhexyl acrylate, n-butyl methacrylate and the like are preferable, and 2-ethylhexyl acrylate is more preferable. One or more (meth) acrylic acid alkyl esters can be used.
　酸無水物としては、例えば、無水コハク酸、無水マレイン酸、無水グルタル酸等が挙げられる。特に無水コハク酸が好ましい。酸無水物は１種または２種以上を使用することができる。 Examples of the acid anhydride include succinic anhydride, maleic anhydride, glutaric anhydride, and the like. Particularly preferred is succinic anhydride. One or more acid anhydrides can be used.
　（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂は、例えば、ポリオレフィン系樹脂を、ラジカル反応条件下にて、酸無水物基を有する不飽和化合物および（メタ）アクリル酸アルキルエステルでグラフト変性することによって得られる（例えば、特開２００２－１７３５１４号公報、特開２００６－２１９６２７号公報等参照）。 Polyolefin resins modified with (meth) acrylic acid alkyl esters and acid anhydrides include, for example, polyolefin resins, unsaturated compounds having acid anhydride groups and alkyl (meth) acrylates under radical reaction conditions. It can be obtained by graft modification with an ester (see, for example, JP-A Nos. 2002-173514 and 2006-219627).
　（メタ）アクリル酸アルキルエステルおよび酸無水物により形成されるグラフト鎖（グラフトポリマー）の数平均分子量は１００以上が好ましく、より好ましくは２００以上、さらに好ましくは３００以上である。（メタ）アクリル酸アルキルエステルによる変性がない場合（すなわち、グラフト鎖に（メタ）アクリル酸アルキルエステル単位が含まれない場合）、適切な長さのグラフト鎖が形成されにくい傾向となる。グラフト鎖（グラフトポリマー）の数平均分子量の平均値が小さすぎる場合、エポキシ樹脂、特にエポキシ変性ポリオレフィン樹脂との架橋構造が形成されにくい傾向となる。グラフト鎖（グラフトポリマー）の数平均分子量の平均値の上限は、本発明の樹脂組成物の封止性能、接着耐湿熱性、耐透湿性等の機能が発揮される限り、特に限定されないが、一般には５０００以下であり、好ましくは３０００以下である。また、グラフト鎖（グラフトポリマー）は（メタ）アクリル酸アルキルエステル単位を２０重量％以上８０重量％以下含有することが好ましく、３０重量％以上７０重量％以下含有することがより好ましく、４０重量％以上６０重量％以下含有することが一層好ましい。 The number average molecular weight of the graft chain (graft polymer) formed from the (meth) acrylic acid alkyl ester and the acid anhydride is preferably 100 or more, more preferably 200 or more, still more preferably 300 or more. When there is no modification by the (meth) acrylic acid alkyl ester (that is, when the (meth) acrylic acid alkyl ester unit is not included in the graft chain), a graft chain having an appropriate length tends not to be formed. When the average value of the number average molecular weight of the graft chain (graft polymer) is too small, it tends to be difficult to form a crosslinked structure with an epoxy resin, particularly an epoxy-modified polyolefin resin. The upper limit of the average value of the number average molecular weight of the graft chain (graft polymer) is not particularly limited as long as the functions of the resin composition of the present invention such as sealing performance, adhesion heat resistance, moisture resistance, etc. are exhibited. Is 5000 or less, preferably 3000 or less. The graft chain (graft polymer) preferably contains (meth) acrylic acid alkyl ester units in an amount of 20 wt% to 80 wt%, more preferably 30 wt% to 70 wt%, more preferably 40 wt%. More preferably, the content is 60% by weight or less.
　グラフト鎖（グラフトポリマー）の数平均分子量は、グラフト変性体の粘度、グラフト変性体の化学構造解析、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法（ポリスチレン換算）などによる分子量測定によって求めることが出来る。ポリオレフィン系樹脂の存在下、（メタ）アクリル酸アルキルエステルおよび酸無水物をラジカル重合して、グラフト変性体が製造される場合、グラフト鎖長は、ポリオレフィン樹脂へのグラフトに寄与していないフリーポリマーの鎖長と同じとみなして、ポリオレフィン系樹脂の主鎖に結合していない、添加した（メタ）アクリル酸アルキルエステルおよび酸無水物のみで形成されるポリマー成分の分子量をＧＰＣ法などで測定することで簡便に求めることができる。ＧＰＣ法による数平均分子量は、具体的には、測定装置として島津製作所社製ＬＣ－９Ａ／ＲＩＤ－６Ａを、カラムとして昭和電工社製Ｓｈｏｄｅｘ Ｋ－８００Ｐ／Ｋ－８０４Ｌ／Ｋ－８０４Ｌを、移動相としてトルエン等を用いて、カラム温度４０℃にて測定し、標準ポリスチレンの検量線を用いて算出することができる。 The number average molecular weight of the graft chain (graft polymer) can be determined by measuring the molecular weight by the viscosity of the graft modified product, chemical structure analysis of the graft modified product, gel permeation chromatography (GPC) method (polystyrene conversion), and the like. When a graft-modified product is produced by radical polymerization of (meth) acrylic acid alkyl ester and acid anhydride in the presence of a polyolefin resin, the graft chain length does not contribute to grafting to the polyolefin resin. The molecular weight of the polymer component formed only from the added (meth) acrylic acid alkyl ester and acid anhydride, which is not bonded to the main chain of the polyolefin resin, is measured by the GPC method or the like. This can be easily obtained. The number average molecular weight by the GPC method is specifically determined by moving LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex® K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column. Using toluene or the like as a phase, the measurement can be made at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.
　（Ａ）成分は１種を使用しても、２種以上を混合して使用してもよい。すなわち、主骨格のポリオレフィン系樹脂および／またはグラフトポリマーが互いに相違する２種以上のグラフト変性体を混合して使用することができる。 (A) A component may be used 1 type or may mix and use 2 or more types. That is, two or more types of graft-modified products having different main-framework polyolefin resins and / or graft polymers can be mixed and used.
　（Ａ）成分が２種以上のグラフト変性体の混合物の場合、以下に記載の（Ａ）成分の酸無水物基の濃度および数平均分子量は、２種以上のグラフト変性体の混合物全体における値であり、また、前記グラフト鎖（グラフトポリマー）の数平均分子量も混合物が有する総グラフトポリマーの数平均分子量である。 In the case where the component (A) is a mixture of two or more types of graft-modified products, the concentration and number average molecular weight of the acid anhydride group of the component (A) described below are values in the entire mixture of two or more types of graft-modified products. In addition, the number average molecular weight of the graft chain (graft polymer) is also the number average molecular weight of the total graft polymer of the mixture.
　（Ａ）成分における、酸無水物基の濃度は、０．０５～１０ｍｍｏｌ／ｇが好ましく、０．１～５ｍｍｏｌ／ｇがより好ましい。酸無水物基の濃度はＪＩＳ Ｋ ２５０１の記載に従い、樹脂１ｇ中に存在する酸を中和するのに必要な水酸化カリウムのｍｇ数として定義される酸価の値より得られる。 The concentration of the acid anhydride group in the component (A) is preferably 0.05 to 10 mmol / g, and more preferably 0.1 to 5 mmol / g. The concentration of the acid anhydride group is obtained from the value of the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of resin according to the description of JIS K2501.
　（Ａ）成分の数平均分子量は特に限定はされないが、樹脂組成物のワニスの良好な塗工性と樹脂組成物における他の成分との良好な相溶性をもたらすという観点から、５０００００以下が好ましく、３０００００以下がより好ましく、１５００００以下が更に好ましい。一方、樹脂組成物のワニスの塗工時のハジキを防止し、形成される樹脂組成物層の耐透湿性を発現させ、機械強度を向上させるという観点から、１００００以上が好ましく、３００００以上がより好ましく、５００００以上が更に好ましい。なお、本発明における数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法（ポリスチレン換算）で測定される。ＧＰＣ法による数平均分子量は、具体的には、測定装置として社島津製作所製ＬＣ－９Ａ／ＲＩＤ－６Ａを、カラムとして昭和電工社製Ｓｈｏｄｅｘ Ｋ－８００Ｐ／Ｋ－８０４Ｌ／Ｋ－８０４Ｌを、移動相としてトルエン等を用いて、カラム温度４０℃にて測定し、標準ポリスチレンの検量線を用いて算出することができる。 The number average molecular weight of the component (A) is not particularly limited, but is preferably 500,000 or less from the viewpoint of providing good coatability of the varnish of the resin composition and good compatibility with other components in the resin composition. 300000 or less is more preferable, and 150,000 or less is still more preferable. On the other hand, it is preferably 10,000 or more, more preferably 30000 or more from the viewpoint of preventing repelling during coating of the varnish of the resin composition, expressing moisture resistance of the formed resin composition layer, and improving mechanical strength. Preferably, 50000 or more is more preferable. In addition, the number average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). The number average molecular weight by the GPC method is specifically determined by moving LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex® K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column. Using toluene or the like as a phase, the measurement can be made at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.
　（Ａ）成分は、加工性を良好なものとする観点から、結晶性が低いものが好ましく、特に非結晶性であることが好ましい。ここで、非結晶性とは、当該（Ａ）成分が明確な融点を有しないことを意味し、例えば、当該（Ａ）成分の融点をＤＳＣ（示差走査熱量測定）で測定した場合に明確なピークが観察されないことである。 The component (A) is preferably low in crystallinity and particularly preferably noncrystalline from the viewpoint of improving workability. Here, non-crystalline means that the component (A) does not have a clear melting point. For example, when the melting point of the component (A) is measured by DSC (differential scanning calorimetry), it is clear. The peak is not observed.
　本発明の樹脂組成物中の（Ａ）成分の含有量は特に制限はないが、樹脂組成物のワニスの良好な塗工性と相溶性をもたらし、形成される樹脂組成物層において良好な湿熱耐性と取り扱い性（タック抑制）を確保できるという観点から、樹脂組成物中の不揮発分を１００質量％とした場合、４５質量％以下が好ましく、４０質量％以下がより好ましく、３５質量％以下が更に好ましい。一方、耐透湿性を向上させ、透明性も向上させるという観点から、樹脂組成物中の不揮発分を１００質量％とした場合、５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上が更に好ましい。 Although there is no restriction | limiting in particular in content of (A) component in the resin composition of this invention, it brings about the favorable coating property and compatibility of the varnish of a resin composition, and favorable wet heat in the resin composition layer formed From the viewpoint of ensuring resistance and handleability (tack suppression), when the nonvolatile content in the resin composition is 100% by mass, it is preferably 45% by mass or less, more preferably 40% by mass or less, and 35% by mass or less. Further preferred. On the other hand, from the viewpoint of improving moisture permeability and improving transparency, when the nonvolatile content in the resin composition is 100% by mass, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 15% by mass. % Or more is more preferable.
＜（Ｂ）エポキシ樹脂＞
　本発明の樹脂組成物は、エポキシ樹脂（以下、「（Ｂ）成分」とも略称する）を含有する。エポキシ樹脂は（Ａ）成分が有する酸無水物基との反応により架橋構造を形成する。エポキシ樹脂としては、特に限定されるものではなく、平均して１分子当り２個以上のエポキシ基を有するものであればよい。例えば、ビスフェノールＡ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、リン含有エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、芳香族グリシジルアミン型エポキシ樹脂（例えば、テトラグリシジルジアミノジフェニルメタン、トリグリシジル－ｐ－アミノフェノール、ジグリシジルトルイジン、ジグリシジルアニリン等）、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ポリアルキレングリコール骨格含有エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、ビスフェノールのジグリシジルエーテル化物、ナフタレンジオールのジグリシジルエーテル化物、フェノール類のグリシジルエーテル化物、およびアルコール類のジグリシジルエーテル化物、並びにこれらのエポキシ樹脂のアルキル置換体、ハロゲン化物および水素添加物等が挙げられる。上記エポキシ樹脂の中では、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、芳香族グリシジルアミン型エポキシ樹脂、ジシクロペンタジエン構造を有するエポキシ樹脂、ポリプロピレングリコール骨格含有エポキシ樹脂等が好ましく、ビスフェノールＡ型エポキシ樹脂、ポリプロピレングリコール骨格含有エポキシ樹脂が特に好ましい。 <(B) Epoxy resin>
The resin composition of the present invention contains an epoxy resin (hereinafter also abbreviated as “component (B)”). An epoxy resin forms a crosslinked structure by reaction with the acid anhydride group which (A) component has. The epoxy resin is not particularly limited as long as it has an average of two or more epoxy groups per molecule. For example, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine Type epoxy resin (for example, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyltoluidine, diglycidylaniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac Type epoxy resin, bisphenol A novolac type epoxy resin, epoxy resin containing polyalkylene glycol skeleton, epoxy resin having butadiene structure, bisphenol And diglycidyl etherified products of naphthalenediol, glycidyl etherified products of phenols, diglycidyl etherified products of alcohols, and alkyl-substituted products, halides and hydrogenated products of these epoxy resins. It is done. Among the above epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy resin, aromatic glycidyl amine type epoxy resin, dicyclopentadiene structure An epoxy resin, a polypropylene glycol skeleton-containing epoxy resin, and the like are preferable, and a bisphenol A type epoxy resin and a polypropylene glycol skeleton-containing epoxy resin are particularly preferable.
　上記エポキシ樹脂の市販品としては、三菱化学社製「８２８ＥＬ」（液状ビスフェノールＡ型エポキシ樹脂）、ＤＩＣ社製「ＨＰ４０３２」、「ＨＰ４０３２Ｄ］（いずれもナフタレン型２官能エポキシ樹脂）、ＤＩＣ社製「ＨＰ４７００」（ナフタレン型４官能エポキシ樹脂）、ＤＩＣ社製「ＨＰ７２００シリーズ」（ジシクロペンタジエン型エポキシ樹脂）、東都化成社製「ＥＳＮ－４７５Ｖ」、「ＥＳＮ－１８５Ｖ」（いずれもナフトール型エポキシ樹脂）、ダイセル化学工業社製「ＰＢ－３６００」（ブタジエン構造を有するエポキシ樹脂）、日本化薬社製「ＮＣ３０００Ｈ」、「ＮＣ３０００Ｌ」、「ＮＣ３１００」、「ＮＣ３０００」、「ＮＣ３０００ＦＨ－７５Ｍ」（いずれもビフェニル型エポキシ樹脂）、三菱化学社製「ＹＸ４０００」（ビフェニル型エポキシ樹脂）、ジャパンエポキシレジン社製「ＹＸ８８００」（アントラセン骨格含有型エポキシ樹脂）、ＤＩＣ社製「ＥＰＩＣＬＯＮ ＥＸＡ４８５０－１０００」（ポリプロピレングリコール骨格含有エポキシ樹脂）、などが挙げられる。 Commercially available epoxy resins include “828EL” (liquid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “HP4032”, “HP4032D” (all naphthalene type bifunctional epoxy resins) manufactured by DIC, and “ "HP4700" (naphthalene type tetrafunctional epoxy resin), DIC's "HP7200 series" (dicyclopentadiene type epoxy resin), Toto Kasei's "ESN-475V", "ESN-185V" (all naphthol type epoxy resins) “PB-3600” (epoxy resin having a butadiene structure) manufactured by Daicel Chemical Industries, Ltd., “NC3000H”, “NC3000L”, “NC3100”, “NC3000”, “NC3000FH-75M” manufactured by Nippon Kayaku Co., Ltd. (all are biphenyl) Type epoxy resin), manufactured by Mitsubishi Chemical Corporation X4000 "(biphenyl type epoxy resin), manufactured by Japan Epoxy Resins Co., Ltd." YX8800 "(anthracene skeleton-containing epoxy resin), DIC Corporation" EPICLON EXA4850-1000 "(polypropylene glycol skeleton-containing epoxy resin), and the like.
　上記エポキシ樹脂は、液状であっても、固体状であってもよく、液状物と固体状物の両方を用いてもよい。ここで、「液状」および「固体状」とは、室温（２５℃）でのエポキシ樹脂の状態である。また、（Ｂ）成分は、エポキシ当量が１００～１５００ｇ／ｅｑの範囲が好ましく、１５０～１０００ｇ／ｅｑの範囲がより好ましく、２００～８００ｇ／ｅｑの範囲が更に好ましい。なお、「エポキシ当量」とは１グラム当量のエポキシ基を含む樹脂のグラム数（g/eq）であり、ＪＩＳ Ｋ ７２３６に規定された方法に従って測定される。 The epoxy resin may be liquid or solid, and both liquid and solid may be used. Here, “liquid” and “solid” are states of the epoxy resin at room temperature (25 ° C.). The component (B) preferably has an epoxy equivalent of 100 to 1500 g / eq, more preferably 150 to 1000 g / eq, and still more preferably 200 to 800 g / eq. The “epoxy equivalent” is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method defined in JIS K 7236.
　かかる（Ｂ）成分のエポキシ樹脂としては、特にエポキシ変性ポリオレフィン系樹脂、すなわち、エポキシ基を有するポリオレフィン樹脂が好ましい。エポキシ変性ポリオレフィン系樹脂としては、例えば、ポリオレフィン系樹脂の主鎖にエポキシ基含有不飽和化合物の単位を含むグラフトポリマーが結合したグラフト変性体が挙げられる。該グラフト変性体は、ポリオレフィン系樹脂を、ラジカル反応条件下で、エポキシ基含有不飽和化合物でグラフト変性することで得られる。エポキシ基含有不飽和化合物としては、グリシジル（メタ）アクリレート、β－メチルグリシジル（メタ）アクリレート、４－ヒドロキシブチルアクリレートグリシジルエーテル、２－ヒドロキシエチルアクリレートグリシジルエーテル、アリルグリシジルエーテル等が挙げられる。好ましくは、グリシジルメタクリレートである。これらは１種または２種以上を使用することができる。また、グラフト変性体におけるポリオレフィン系樹脂の具体例としては、（Ａ）成分におけるポリオレフィン系樹脂の具体例として例示したものと同じものが挙げられる。 As the epoxy resin as the component (B), an epoxy-modified polyolefin resin, that is, a polyolefin resin having an epoxy group is particularly preferable. Examples of the epoxy-modified polyolefin resin include a graft-modified product in which a graft polymer containing a unit of an epoxy group-containing unsaturated compound is bonded to the main chain of the polyolefin resin. The graft-modified product can be obtained by graft-modifying a polyolefin resin with an epoxy group-containing unsaturated compound under radical reaction conditions. Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, 2-hydroxyethyl acrylate glycidyl ether, and allyl glycidyl ether. Preferably, it is glycidyl methacrylate. These can use 1 type (s) or 2 or more types. Specific examples of the polyolefin-based resin in the graft-modified product include the same as those exemplified as specific examples of the polyolefin-based resin in the component (A).
　また、エポキシ変性ポリオレフィン系樹脂としては、上記のエポキシ基含有不飽和化合物から選ばれる１種または２種以上と、１種または２種以上のオレフィンとをラジカル共重合して、エポキシ基含有不飽和化合物単位とオレフィン単位を含む共重合体として得るようにしてもよい。該オレフィンの具体例としては、前述の（Ａ）成分の変性ポリオレフィン系樹脂における主骨格のポリオレフィン系樹脂の構成単量体単位として例示したものと同じものを挙げることができる。 In addition, as the epoxy-modified polyolefin-based resin, one or two or more kinds selected from the above epoxy group-containing unsaturated compounds and one or two or more olefins are radically copolymerized to obtain an epoxy group-containing unsaturated resin. You may make it obtain as a copolymer containing a compound unit and an olefin unit. Specific examples of the olefin include the same examples as the constituent monomer units of the polyolefin resin having the main skeleton in the modified polyolefin resin of the component (A).
　エポキシ変性ポリオレフィン系樹脂におけるエポキシ基の濃度は、０．０５～１０ｍｍｏｌ／ｇが好ましく、０．１～５ｍｍｏｌ／ｇがより好ましい。エポキシ基濃度はＪＩＳ Ｋ ７２３６－１９９５に基づいて得られるエポキシ当量から求められる。 The concentration of the epoxy group in the epoxy-modified polyolefin resin is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g. The epoxy group concentration is determined from the epoxy equivalent obtained based on JIS K 7236-1995.
　エポキシ変性ポリオレフィン系樹脂の数平均分子量は特に限定はされないが、樹脂組成物のワニスの良好な塗工性と樹脂組成物における他の成分との良好な相溶性をもたらすという観点から、５０００００以下が好ましく、３０００００以下がより好ましく、１５００００以下が更に好ましい。一方、樹脂組成物のワニスの塗工時のハジキを防止し、形成される樹脂組成物層の耐透湿性を発現させ、機械強度を向上させるという観点から、１００００以上が好ましく、３００００以上がより好ましく、５００００以上が更に好ましい。なお、ここでいう数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法（ポリスチレン換算）で測定される。ＧＰＣ法による数平均分子量は、具体的には、測定装置として社島津製作所製ＬＣ－９Ａ／ＲＩＤ－６Ａを、カラムとして昭和電工社製Ｓｈｏｄｅｘ Ｋ－８００Ｐ／Ｋ－８０４Ｌ／Ｋ－８０４Ｌを、移動相としてトルエン等を用いて、カラム温度４０℃にて測定し、標準ポリスチレンの検量線を用いて算出することができる。 The number average molecular weight of the epoxy-modified polyolefin resin is not particularly limited, but from the viewpoint of providing good coatability of the varnish of the resin composition and good compatibility with other components in the resin composition, it is 500,000 or less. Preferably, 300,000 or less is more preferable, and 150,000 or less is still more preferable. On the other hand, it is preferably 10,000 or more, more preferably 30000 or more from the viewpoint of preventing repelling during coating of the varnish of the resin composition, expressing moisture resistance of the formed resin composition layer, and improving mechanical strength. Preferably, 50000 or more is more preferable. In addition, the number average molecular weight here is measured by a gel permeation chromatography (GPC) method (polystyrene conversion). The number average molecular weight by the GPC method is specifically determined by moving LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex® K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column. Using toluene or the like as a phase, the measurement can be made at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.
　エポキシ変性ポリオレフィン系樹脂は、加工性を良好なものとする観点から、結晶性が低いものが好ましく、特に非結晶性であることが好ましい。ここで、非結晶性とは、当該エポキシ変性ポリオレフィン系樹脂が明確な融点を有しないことを意味し、例えば、当該エポキシ変性ポリオレフィン系樹脂のＤＳＣ（示差走査熱量測定）で融点を測定した場合に明確なピークが観察されないことである。 The epoxy-modified polyolefin-based resin preferably has low crystallinity from the viewpoint of improving processability, and is particularly preferably amorphous. Here, non-crystalline means that the epoxy-modified polyolefin resin does not have a clear melting point, for example, when the melting point is measured by DSC (differential scanning calorimetry) of the epoxy-modified polyolefin resin. A clear peak is not observed.
　（Ｂ）成分は１種または２種以上組み合わせて使用してもよい。樹脂組成物中の（Ｂ）成分の含有量は特に制限はないが、良好な耐透湿性を確保できるという観点から、樹脂組成物中の不揮発分を１００質量％とした場合、４５質量％以下が好ましく、４０質量％以下がより好ましく、３５質量％以下が更に好ましい。一方、良好な取り扱い性（タック抑制）を確保できるという観点から、樹脂組成物中の不揮発分を１００質量％とした場合、５質量以上％が好ましく、１０質量％以上がより好ましく、１５質量％以上が更に好ましい。 (B) Component may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in content of (B) component in a resin composition, From a viewpoint that favorable moisture-permeable resistance can be ensured, when the non volatile matter in a resin composition is 100 mass%, it is 45 mass% or less. Is preferable, 40 mass% or less is more preferable, and 35 mass% or less is still more preferable. On the other hand, from the viewpoint of ensuring good handleability (tack suppression), when the nonvolatile content in the resin composition is 100% by mass, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 15% by mass. The above is more preferable.
　本発明の樹脂組成物中の（Ａ）成分と（Ｂ）成分の量比は、本発明の効果が発揮される範囲で任意に選ばれるが、良好な架橋構造を形成し、未反応の活性な官能基の含有量を減らし、安定的に性能を発揮させる観点から、（Ａ）成分の酸無水物当量（Ｅａ）と（Ｂ）成分のエポキシ当量（Ｅｂ）との比（Ｅａ／Ｅｂ）が、好ましくは０．７～１．４５、より好ましくは０．８～１．２５、さらに好ましくは０．９～１．１５、一層好ましくは０．９５～１．０６となる比である。なお、「酸無水物当量」とは１グラム当量の酸無水物基を含む樹脂のグラム数（g/eq）である。 The amount ratio of the component (A) and the component (B) in the resin composition of the present invention is arbitrarily selected within the range in which the effect of the present invention is exerted, but forms a good cross-linked structure and unreacted activity. From the viewpoint of reducing the content of functional groups and exhibiting performance stably, the ratio of the acid anhydride equivalent (Ea) of the component (A) to the epoxy equivalent (Eb) of the component (B) (Ea / Eb) However, the ratio is preferably 0.7 to 1.45, more preferably 0.8 to 1.25, still more preferably 0.9 to 1.15, and still more preferably 0.95 to 1.06. The “acid anhydride equivalent” is the number of grams (g / eq) of a resin containing 1 gram equivalent of an acid anhydride group.
　本発明の樹脂組成物において、（Ａ）成分と（Ｂ）成分の合計含有量は、特に制限はされないが、接着性、加工性等の観点から、樹脂組成物中の不揮発分を１００質量％とした場合、８０質量％以下が好ましく、７５質量％以下がより好ましく、７０質量％以下が更に好ましい。一方、湿熱耐性の観点から、樹脂組成物中の不揮発分を１００質量％とした場合、５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上が更に好ましい。 In the resin composition of the present invention, the total content of the component (A) and the component (B) is not particularly limited, but from the viewpoint of adhesiveness, workability, etc., the nonvolatile content in the resin composition is 100% by mass. 80 mass% or less is preferable, 75 mass% or less is more preferable, and 70 mass% or less is still more preferable. On the other hand, from the viewpoint of wet heat resistance, when the nonvolatile content in the resin composition is 100% by mass, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 15% by mass or more is even more preferable.
＜（Ｃ）粘着付与樹脂＞
　本発明において使用される（Ｃ）粘着付与樹脂（以下、「（Ｃ）成分」とも略称する）は、タッキファイヤーとも呼ばれ、可塑性高分子に配合して粘着性を付与させる樹脂である。（Ｃ）成分としては、特に限定されるものではなく、テルペン樹脂、変性テルペン樹脂（水素添加テルペン樹脂、テルペンフェノール共重合樹脂、芳香族変性テルペン樹脂等）、クマロン樹脂、インデン樹脂、石油樹脂（脂肪族系石油樹脂、水添脂環式石油樹脂、芳香族系石油樹脂、脂肪族芳香族共重合系石油樹脂、脂環族系石油樹脂、ジシクロペンタジエン系石油樹脂およびその水素化物等）が好ましく使用される。 <(C) Tackifying resin>
The (C) tackifier resin (hereinafter also abbreviated as “component (C)”) used in the present invention is also called a tackifier and is a resin that is added to a plastic polymer to impart tackiness. The component (C) is not particularly limited, and includes terpene resins, modified terpene resins (hydrogenated terpene resins, terpene phenol copolymer resins, aromatic modified terpene resins, etc.), coumarone resins, indene resins, petroleum resins ( Aliphatic petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene petroleum resins and their hydrides) Preferably used.
　なかでも、樹脂組成物の接着性、耐透湿性、相溶性等の観点から、テルペン樹脂、芳香族変性テルペン樹脂、テルペンフェノール共重合樹脂、水添脂環式石油樹脂、芳香族系石油樹脂、脂肪族芳香族共重合系石油樹脂、脂環族系石油樹脂がより好ましく、脂環族系石油樹脂が更に好ましく、脂環族飽和炭化水素樹脂が更に一層好ましく、シクロヘキサン環含有飽和炭化水素樹脂、ジシクロペンタジエン変性炭化水素樹脂が特に好ましい。 Among them, from the viewpoint of adhesiveness, moisture permeability, compatibility, etc. of the resin composition, terpene resin, aromatic modified terpene resin, terpene phenol copolymer resin, hydrogenated alicyclic petroleum resin, aromatic petroleum resin, Aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins are more preferred, alicyclic petroleum resins are more preferred, alicyclic saturated hydrocarbon resins are even more preferred, cyclohexane ring-containing saturated hydrocarbon resins, Dicyclopentadiene-modified hydrocarbon resin is particularly preferred.
　（Ｃ）成分として使用できる市販品としては、テルペン樹脂として、ＹＳレジンＰＸ、ＹＳレジンＰＸＮ（いずれもヤスハラケミカル社製）等が挙げられ、芳香族変性テルペン樹脂として、ＹＳレジンＴＯ、ＴＲシリーズ（いずれもヤスハラケミカル社製）等が挙げられ、水素添加テルペン樹脂として、クリアロンＰ、クリアロンＭ、クリアロンＫシリーズ（いずれもヤスハラケミカル社製）等が挙げられ、テルペンフェノール共重合樹脂として、ＹＳポリスター２０００、ポリスターＵ、ポリスターＴ、ポリスターＳ、マイティエースＧ（いずれもヤスハラケミカル社製）等が挙げられ、水添脂環式石油樹脂として、Ｅｓｃｏｒｅｚ５３００シリーズ、５６００シリーズ（いずれもエクソンモービル社製）等が挙げられ、芳香族系石油樹脂としてＥＮＤＥＸ１５５（イーストマン社製）等が挙げられ、脂肪族芳香族共重合系石油樹脂としてＱｕｉｎｔｏｎｅＤ１００（日本ゼオン社製）等が挙げられ、脂環族系石油樹脂としてＱｕｉｎｔｏｎｅ１３２５、Ｑｕｉｎｔｏｎｅ１３４５（いずれも日本ゼオン社製）等が挙げられ、水添脂環式石油樹脂としてアルコンＰ１００、アルコンＰ１２５、アルコンＰ１４０（いずれも荒川化学社製）等が挙げられ、シクロヘキサン環含有飽和炭化水素樹脂としてＴＦＳ１３－０３０（荒川化学社製）等が挙げられる。 Examples of commercially available products that can be used as component (C) include terpene resins such as YS resin PX and YS resin PXN (both manufactured by Yasuhara Chemical Co., Ltd.), and aromatic-modified terpene resins such as YS resin TO and TR series (any Are Yasuhara Chemical Co., Ltd.), and hydrogenated terpene resins include Clearon P, Clearon M, Clearon K series (all manufactured by Yasuhara Chemical Co., Ltd.), and terpene phenol copolymer resins are YS Polystar 2000, Polystar U. , Polystar T, Polystar S, Mighty Ace G (all manufactured by Yashara Chemical Co., Ltd.), etc., and hydrogenated alicyclic petroleum resins include Escorez 5300 series, 5600 series (all manufactured by ExxonMobil Corp.), etc. Tribe oil tree ENDEX155 (manufactured by Eastman Co., Ltd.) and the like, quintone D100 (manufactured by Nippon Zeon Co., Ltd.) and the like as aliphatic aromatic copolymer petroleum resins, and quintone 1325 and quintone 1345 (both from Nippon Zeon) as alicyclic petroleum resins. Alcon P100, Alcon P125, Alcon P140 (all manufactured by Arakawa Chemical Co., Ltd.) and the like are listed as hydrogenated alicyclic petroleum resins, and TFS13-030 (Arakawa) is a cyclohexane ring-containing saturated hydrocarbon resin. Chemical Co., Ltd.).
　（Ｃ）成分の軟化点は、樹脂組成物シートの積層工程でシートが軟化し、かつ所望の耐熱性を持つという観点から、５０～２００℃が好ましく、９０～１８０℃がより好ましく、１００～１５０℃が更に好ましい。なお、軟化点の測定は、ＪＩＳ Ｋ２２０７に従い環球法により測定される。 The softening point of the component (C) is preferably from 50 to 200 ° C., more preferably from 90 to 180 ° C., from the viewpoint that the sheet softens in the resin composition sheet lamination step and has the desired heat resistance. 150 ° C. is more preferable. The softening point is measured by the ring and ball method according to JIS K2207.
　（Ｃ）成分は１種または２種以上を組み合わせて使用してもよい。樹脂組成物中の（Ｃ）成分の含有量は特に制限はないが、樹脂組成物の良好な耐透湿性を維持するという観点から、樹脂組成物中の不揮発分を１００質量％とした場合、８０質量％以下が好ましく、６０質量％以下がより好ましく、５０質量％以下が更に好ましい。一方、十分な接着性を有するという観点から、樹脂組成物中の不揮発分を１００質量％とした場合、５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上が更に好ましい。 (C) Component may be used alone or in combination of two or more. The content of the component (C) in the resin composition is not particularly limited, but from the viewpoint of maintaining good moisture resistance of the resin composition, when the nonvolatile content in the resin composition is 100% by mass, 80 mass% or less is preferable, 60 mass% or less is more preferable, and 50 mass% or less is still more preferable. On the other hand, from the viewpoint of having sufficient adhesiveness, when the nonvolatile content in the resin composition is 100% by mass, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 15% by mass or more is even more preferable.
　本発明の参考例となる封止用樹脂組成物の態様として、以下の樹脂組成物が挙げられる。すなわち、酸無水物基及び／又はエポキシ基を有する、ポリオレフィン系樹脂、及び、粘着付与樹脂を含有する封止用樹脂組成物、好ましくは、酸無水物基を有するポリオレフィン系樹脂及びエポキシ基を有するポリオレフィン系樹脂、並びに粘着付与樹脂を含有する封止用樹脂組成物が挙げられる。酸無水物基を有するポリオレフィン系樹脂は、酸無水物変性により酸無水物基を有する樹脂であれば特に限定はなく、上記（Ａ）成分の（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂でもよく、またその他の変性により他の官能基を含んでいてもよい。すなわち、「酸無水物基を有するポリオレフィン系樹脂」は、（メタ）アクリル酸アルキルエステル変性を必須としない点を除き、その他の特徴は上記（Ａ）成分の（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂に踏襲される。例えば、ポリオレフィン系樹脂は共重合体であってもよく、共重合体の具体例としては、例えば、エチレン－非共役ジエン共重合体、エチレン－ブテン共重合体、エチレン－ブテン－非共役ジエン共重合体、エチレン－プロピレン共重合体、エチレン－プロピレン－非共役ジエン共重合体、エチレン－プロピレン－ブテン共重合体、プロピレン－ブテン共重合体、プロピレン－ブテン－非共役ジエン共重合体、イソブチレン－ブテン共重合体、イソブチレン－ブテン－非共役ジエン共重合体、スチレン－イソブチレン共重合体、スチレン－イソブチレン－スチレン共重合体等が挙げられる。また、粘着付与樹脂は上記（Ｃ）成分の粘着付与樹脂と同義である。酸無水物基及び／又はエポキシ基を有する、ポリオレフィン系樹脂の酸無水物基及び／又はエポキシ基の官能基濃度は０．０５～１０ｍｍｏｌ／ｇが好ましい。酸無水物基及び／又はエポキシ基を有する、プロピレン－ブテン共重合体の含有量が、樹脂組成物中の不揮発分の合計１００質量％当たり、３５～８０質量％であるのが好ましい。ここにおける封止用樹脂組成物は好ましくは 有機ＥＬ素子の封止用に用いることができる。ここにおける封止材用樹脂組成物は封止用シートの形態で、例えば有機ＥＬ封止用に用いることができる。 The following resin composition is mentioned as an aspect of the sealing resin composition which is a reference example of the present invention. That is, the resin composition for sealing containing the polyolefin resin which has an acid anhydride group and / or an epoxy group, and tackifying resin, Preferably, it has the polyolefin resin which has an acid anhydride group, and an epoxy group An encapsulating resin composition containing a polyolefin-based resin and a tackifying resin is exemplified. The polyolefin resin having an acid anhydride group is not particularly limited as long as it is a resin having an acid anhydride group by acid anhydride modification, and is modified with the (meth) acrylic acid alkyl ester and acid anhydride of the component (A). May be a polyolefin-based resin, and may contain other functional groups by other modifications. That is, the “polyolefin resin having an acid anhydride group” is characterized in that the (meth) acrylic acid alkyl ester of the component (A) and the acid are other than that the (meth) acrylic acid alkyl ester modification is not essential. Followed by polyolefin resin modified with anhydride. For example, the polyolefin resin may be a copolymer, and specific examples of the copolymer include, for example, an ethylene-nonconjugated diene copolymer, an ethylene-butene copolymer, and an ethylene-butene-nonconjugated diene copolymer. Polymer, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-propylene-butene copolymer, propylene-butene copolymer, propylene-butene-nonconjugated diene copolymer, isobutylene- Examples include butene copolymers, isobutylene-butene-nonconjugated diene copolymers, styrene-isobutylene copolymers, and styrene-isobutylene-styrene copolymers. Moreover, tackifying resin is synonymous with the tackifying resin of the said (C) component. The functional group concentration of the acid anhydride group and / or epoxy group of the polyolefin resin having an acid anhydride group and / or epoxy group is preferably 0.05 to 10 mmol / g. The content of the propylene-butene copolymer having an acid anhydride group and / or an epoxy group is preferably 35 to 80% by mass per 100% by mass of the total nonvolatile content in the resin composition. The sealing resin composition here can preferably be used for sealing organic EL elements. The resin composition for sealing materials here is in the form of a sealing sheet and can be used, for example, for organic EL sealing.
＜硬化促進剤＞
　本発明の樹脂組成物（上記（Ａ）～（Ｃ）成分を含有する樹脂組成物）及び上記参考例の樹脂組成物には、良好な架橋構造を形成させる観点から、更に硬化促進剤を含有させてもよい。硬化促進剤としては、特に限定はされないが、アミン系硬化促進剤、グアニジン系硬化促進剤、イミダゾール系硬化促進剤、ホスホニウム系硬化促進剤などが挙げられる。硬化促進剤は１種または２種以上組み合わせて使用してもよい。 <Curing accelerator>
The resin composition of the present invention (resin composition containing the above components (A) to (C)) and the resin composition of the above reference examples further contain a curing accelerator from the viewpoint of forming a good crosslinked structure. You may let them. Although it does not specifically limit as a hardening accelerator, An amine hardening accelerator, a guanidine hardening accelerator, an imidazole hardening accelerator, a phosphonium hardening accelerator, etc. are mentioned. You may use a hardening accelerator 1 type or in combination of 2 or more types.
　アミン系硬化促進剤としては、特に制限はないが、テトラメチルアンモニウムブロマイド、テトラブチルアンモニウムブロマイド等の４級アンモニウム塩；ＤＢＵ（１，８－ジアザビシクロ［５．４．０]ウンデセン－７）、ＤＢＮ（１，５－ジアザビシクロ[４．３．０]ノネン－５）、ＤＢＵ－フェノール塩、ＤＢＵ－オクチル酸塩、ＤＢＵ－ｐ－トルエンスルホン酸塩、ＤＢＵ－ギ酸塩、ＤＢＵ－フェノールノボラック樹脂塩等のジアザビシクロ化合物；ベンジルジメチルアミン、２－（ジメチルアミノメチル）フェノール、２，４，６－トリス（ジメチルアミノメチル）フェノール等の３級アミンおよびそれらの塩、芳香族ジメチルウレア、脂肪族ジメチルウレア、芳香族ジメチルウレア等のジメチルウレア化合物；等が挙げられる。これらは１種または２種以上組み合わせて使用してもよい。 The amine curing accelerator is not particularly limited, but includes quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide; DBU (1,8-diazabicyclo [5.4.0] undecene-7), DBN (1,5-diazabicyclo [4.3.0] nonene-5), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, DBU-phenol novolac resin salt, etc. Diazabicyclo compounds of the following: tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol and their salts, aromatic dimethylurea, aliphatic dimethylurea, And dimethylurea compounds such as aromatic dimethylurea; You may use these 1 type or in combination of 2 or more types.
　グアニジン系硬化促進剤としては、特に制限はないが、ジシアンジアミド、１－メチルグアニジン、１－エチルグアニジン、１－シクロヘキシルグアニジン、１－フェニルグアニジン、１－（ｏ－トリル）グアニジン、ジメチルグアニジン、ジフェニルグアニジン、トリメチルグアニジン、テトラメチルグアニジン、ペンタメチルグアニジン、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、１－メチルビグアニド、１－エチルビグアニド、１-ｎ－ブチルビグアニド、１－ｎ－オクタデシルビグアニド、１，１－ジメチルビグアニド、１，１－ジエチルビグアニド、１－シクロヘキシルビグアニド、１－アリルビグアニド、１－フェニルビグアニド、１－（ｏ－トリル）ビグアニド等が挙げられる。これらは１種または２種以上組み合わせて使用してもよい。 The guanidine curing accelerator is not particularly limited, but dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4. 4.0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1- Cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide And 1- (o-tolyl) biguanide. You may use these 1 type or in combination of 2 or more types.
　イミダゾール系硬化促進剤としては、特に制限はないが、１Ｈ－イミダゾール、２－メチル-イミダゾール、２－フェニル－４－メチルイミダゾール、１－シアノエチルー２－エチル－４－メチル－イミダゾール、２－フェニル－４，５－ビス（ヒドロキシメチル）－イミダゾール、１－ベンジル－２－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニル－イミダゾール、２－ドデシル－イミダゾール、２－ヘプタデシルイミダゾール、１，２－ジメチル－イミダゾール等が挙げられる。これらは１種または２種以上組み合わせて使用してもよい。 The imidazole curing accelerator is not particularly limited, but 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl-imidazole, 2-phenyl- 4,5-bis (hydroxymethyl) -imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-imidazole, 2-dodecyl-imidazole 2-heptadecylimidazole, 1,2-dimethyl-imidazole and the like. You may use these 1 type or in combination of 2 or more types.
　ホスホニウム系硬化促進剤としては、特に制限はないが、トリフェニルホスフィン、ホスホニウムボレート化合物、テトラフェニルホスホニウムテトラフェニルボレート、ｎ－ブチルホスホニウムテトラフェニルボレート、テトラブチルホスホニウムデカン酸塩、（４－メチルフェニル）トリフェニルホスホニウムチオシアネート、テトラフェニルホスホニウムチオシアネート、ブチルトリフェニルホスホニウムチオシアネート等が挙げられる。これらは１種または２種以上組み合わせて使用してもよい。 The phosphonium curing accelerator is not particularly limited, but triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) Examples include triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. You may use these 1 type or in combination of 2 or more types.
　硬化促進剤は１種または２種以上を組み合わせて使用してもよい。樹脂組成物中の硬化促進剤の含有量は特に制限はないが、耐透湿性の低下を防止するという観点から、樹脂組成物中の不揮発分を１００質量％とした場合、５質量％以下が好ましく、１質量％以下がより好ましい。一方、タックを抑制させるという観点から、樹脂組成物中の不揮発分を１００質量％とした場合、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましい。  The curing accelerator may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in content of the hardening accelerator in a resin composition, From a viewpoint of preventing the fall of moisture permeability resistance, when the non volatile matter in a resin composition is 100 mass%, 5 mass% or less is Preferably, 1 mass% or less is more preferable. On the other hand, from the viewpoint of suppressing tackiness, when the nonvolatile content in the resin composition is 100% by mass, 0.01% by mass or more is preferable, and 0.05% by mass or more is more preferable.
＜吸湿性金属化合物＞
　本発明の樹脂組成物は、耐透湿性をより向上させるために、さらに吸湿性金属酸化物を含有させることができる。ここで、「吸湿性金属酸化物」とは、水分を吸収する能力をもち、吸湿した水分と化学反応して水酸化物になる金属酸化物を意味する。具体的には、酸化カルシウム、酸化マグネシウム、酸化ストロンチウム、酸化アルミニウム、酸化バリウム等から選ばれる１種か、または、２種以上の混合物若しくは固溶物である。２種以上の混合物若しくは固溶物の例としては、具体的には、焼成ドロマイト（酸化カルシウムおよび酸化マグネシウムを含む混合物）、焼成ハイドロタルサイト（酸化カルシウムと酸化アルミニウムの固溶物）等が挙げられる。中でも、吸湿性が高い点、コスト、原料の安定性の点から、酸化カルシウム、酸化マグネシウム、焼成ハイドロタルサイトが好ましく、より好ましくは焼成ハイドロタルサイトである。焼成ハイドロタルサイトは、天然ハイドロタルサイト（Ｍｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ）および合成ハイドロタルサイト（ハイドロタルサイト様化合物）を焼成して化学構造中のＯＨ量を減少乃至消失させたものである。また、樹脂組成物の硬化体の透明性を向上させる観点から、ＢＥＴ比表面積６５ｍ２/ｇ以上の焼成ハイドロタルサイトが特に好ましい。ＢＥＴ比表面積６５ｍ２/ｇ以上の焼成ハイドロタルサイトは、ＢＥＴ比表面積が８０ｍ２/ｇ以上が好ましく、１００ｍ２/ｇ以上がより好ましい。また、ＢＥＴ比表面積が２００ｍ２/ｇ以下が好ましく、１５０ｍ２/ｇ以下がより好ましい。 <Hygroscopic metal compound>
The resin composition of the present invention can further contain a hygroscopic metal oxide in order to further improve the moisture permeability resistance. Here, the “hygroscopic metal oxide” means a metal oxide that has a capability of absorbing moisture and chemically reacts with moisture that has been absorbed to become a hydroxide. Specifically, it is one kind selected from calcium oxide, magnesium oxide, strontium oxide, aluminum oxide, barium oxide and the like, or a mixture or solid solution of two or more kinds. Specific examples of the mixture or solid solution of two or more kinds include calcined dolomite (a mixture containing calcium oxide and magnesium oxide), calcined hydrotalcite (solid solution of calcium oxide and aluminum oxide), and the like. It is done. Among these, calcium oxide, magnesium oxide, and calcined hydrotalcite are preferable from the viewpoint of high hygroscopicity, cost, and stability of raw materials, and calcined hydrotalcite is more preferable. The calcined hydrotalcite reduces the amount of OH in the chemical structure by calcining natural hydrotalcite (Mg 6 Al 2 (OH) 16 CO 3 · 4H 2 O) and synthetic hydrotalcite (hydrotalcite-like compound) Or disappeared. Further, from the viewpoint of improving the transparency of the cured product of the resin composition, a calcined hydrotalcite having a BET specific surface area of 65 m 2 / g or more is particularly preferable. The calcined hydrotalcite having a BET specific surface area of 65 m 2 / g or more preferably has a BET specific surface area of 80 m 2 / g or more, and more preferably 100 m 2 / g or more. Further, BET specific surface area is preferably from 200m 2 / g, more preferably at most 150m 2 / g.
　吸湿性金属酸化物は、種々の技術分野において吸湿材として公知であり、市販品を使用することができる。具体的には、酸化カルシウム（三共製粉社製「モイストップ＃１０」等）、酸化マグネシウム（協和化学工業社製「キョーワマグＭＦ－１５０」、「キョーワマグＭＦ－３０」、タテホ化学工業社製「ピュアマグＦＮＭＧ」等）、軽焼酸化マグネシウム（タテホ化学工業社製の「TATEHOMAG＃５００」、「TATEHOMAG＃１０００」、TATEHOMAG＃５０００」等）、焼成ドロマイト（吉澤石灰社製「ＫＴ」等）、焼成ハイドロタルサイト（協和化学工業社製「ＤＨＴ－４Ａ」、ＤＨＴ－４Ａ－２、ＤＨＴ－４Ｃ等）等が挙げられる。 The hygroscopic metal oxide is known as a hygroscopic material in various technical fields, and a commercially available product can be used. Specifically, calcium oxide (“Moystop # 10” manufactured by Sankyo Flour Milling Co., Ltd.), magnesium oxide (“Kyowa Mag MF-150”, “Kyowa Mag MF-30” manufactured by Kyowa Chemical Industry Co., Ltd., “Pure Mag” manufactured by Tateho Chemical Industry Co., Ltd. FNMG ”, etc.), lightly burned magnesium oxide (“ TATEHOMAG # 500 ”,“ TATEHOMAG # 1000 ”, TATEHOMAG # 5000”, etc. manufactured by Tateho Chemical Industries, Ltd.), calcined dolomite (“KT”, etc., produced by Yoshizawa Lime), calcined hydro And talcite (“DHT-4A”, DHT-4A-2, DHT-4C, etc., manufactured by Kyowa Chemical Industry Co., Ltd.).
　吸湿性金属酸化物は、表面処理剤で表面処理したものを用いることができる。表面処理に使用する表面処理剤としては、例えば、高級脂肪酸、アルキルシラン類、シランカップリング剤等を使用することができ、なかでも、高級脂肪酸、アルキルシラン類が好適である。表面処理剤は、１種または２種以上を使用できる。 As the hygroscopic metal oxide, a surface treated with a surface treatment agent can be used. As the surface treatment agent used for the surface treatment, for example, higher fatty acids, alkylsilanes, silane coupling agents and the like can be used, and among these, higher fatty acids and alkylsilanes are preferable. One or more surface treatment agents can be used.
　高級脂肪酸としては、例えば、ステアリン酸、モンタン酸、ミリスチン酸、パルミチン酸などの炭素数１８以上の高級脂肪酸が挙げられ、中でも、ステアリン酸が好ましい。これらは１種または２種以上組み合わせて使用してもよい。アルキルシラン類としては、メチルトリメトキシシラン、エチルトリメトキシシラン、ヘキシルトリメトキシシラン、オクチルトリメトキシシラン、デシルトリメトキシシラン、オクタデシルトリメトキシシラン、ジメチルジメトキシシラン、オクチルトリエトキシシラン、ｎ－オクタデシルジメチル（３－（トリメトキシシリル）プロピル）アンモニウムクロライド等が挙げられる。これらは１種または２種以上組み合わせて使用してもよい。シランカップリング剤としては、例えば、３－グリシジルオキシプロピルトリメトキシシラン、３－グリシジルオキシプロピルトリエトキシシラン、３－グリシジルオキシプロピル（ジメトキシ）メチルシランおよび２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシランなどのエポキシ系シランカップリング剤；３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン、３－メルカプトプロピルメチルジメトキシシランおよび１１－メルカプトウンデシルトリメトキシシランなどのメルカプト系シランカップリング剤；３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－アミノプロピルジメトキシメチルシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－メチルアミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシランおよびＮ－（２－アミノエチル）－３－アミノプロピルジメトキシメチルシランなどのアミノ系シランカップリング剤；３－ウレイドプロピルトリエトキシシランなどのウレイド系シランカップリング剤、ビニルトリメトキシシラン、ビニルトリエトキシシランおよびビニルメチルジエトキシシランなどのビニル系シランカップリング剤；ｐ－スチリルトリメトキシシランなどのスチリル系シランカップリング剤；３－アクリルオキシプロピルトリメトキシシランおよび３－メタクリルオキシプロピルトリメトキシシランなどのアクリレート系シランカップリング剤；３－イソシアネートプロピルトリメトキシシランなどのイソシアネート系シランカップリング剤、ビス（トリエトキシシリルプロピル）ジスルフィド、ビス（トリエトキシシリルプロピル）テトラスルフィドなどのスルフィド系シランカップリング剤；フェニルトリメトキシシラン、メタクリロキシプロピルトリメトキシシラン、イミダゾールシラン、トリアジンシラン等を挙げることができる。これらは１種または２種以上組み合わせて使用してもよい。 Examples of the higher fatty acid include higher fatty acids having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid, and palmitic acid, among which stearic acid is preferable. You may use these 1 type or in combination of 2 or more types. Alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl ( And 3- (trimethoxysilyl) propyl) ammonium chloride. You may use these 1 type or in combination of 2 or more types. Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Epoxy silane coupling agents such as silane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane ; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltri Amino-based silane cups such as toxisilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Ringing agents; Ureido silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; p-styryltrimethoxysilane Styryl-based silane coupling agents; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; 3-isocyanatopropyltrimeth Isocyanate silane coupling agents such as silane, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole Examples thereof include silane and triazine silane. You may use these 1 type or in combination of 2 or more types.
　吸湿性金属酸化物の表面処理は、例えば、未処理の吸湿性金属酸化物を混合機で常温にて攪拌分散させながら、表面処理剤を添加噴霧して５～６０分間攪拌することによって行なうことができる。混合機としては、公知の混合機を使用することができ、例えば、Ｖブレンダー、リボンブレンダー、バブルコーンブレンダー等のブレンダー、ヘンシェルミキサーおよびコンクリートミキサー等のミキサー、ボールミル、カッターミル等が挙げられる。又、ボールミルなどで吸湿材を粉砕する際に、前記の高級脂肪酸、アルキルシラン類またはシランカップリング剤を混合し、表面処理する方法も可能である。表面処理剤の処理量は吸湿性金属酸化物の種類または表面処理剤の種類等によっても異なるが、吸湿性金属酸化物に対して１～１０質量％が好ましい。 The surface treatment of the hygroscopic metal oxide is performed, for example, by adding and spraying the surface treatment agent and stirring for 5 to 60 minutes while stirring and dispersing the untreated hygroscopic metal oxide at room temperature with a mixer. Can do. As a mixer, a well-known mixer can be used, For example, blenders, such as V blender, a ribbon blender, and a bubble cone blender, mixers, such as a Henschel mixer and a concrete mixer, a ball mill, a cutter mill, etc. are mentioned. Further, when the hygroscopic material is pulverized with a ball mill or the like, a method of surface treatment by mixing the above-mentioned higher fatty acid, alkylsilanes or silane coupling agent is also possible. The treatment amount of the surface treatment agent varies depending on the type of the hygroscopic metal oxide or the type of the surface treatment agent, but is preferably 1 to 10% by mass with respect to the hygroscopic metal oxide.
　吸湿性金属酸化物は１種または２種以上を組み合わせて使用してもよい。本発明の樹脂組成物が吸湿性金属化合物を含有する場合、その含有量は特に限定されるものではないが、硬化物の強度が低下して脆くなるのを防止するという観点から、樹脂組成物中の不揮発分１００質量％に対し、５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下が更に好ましい。また、吸湿性金属酸化物を配合することの効果を十分得るという観点から、樹脂組成物中の不揮発分１００質量％に対し、１質量％以上が好ましく、５質量％以上がより好ましく、１０質量％以上が更に好ましい。 Hygroscopic metal oxides may be used alone or in combination of two or more. When the resin composition of the present invention contains a hygroscopic metal compound, its content is not particularly limited, but from the viewpoint of preventing the strength of the cured product from being reduced and becoming brittle, the resin composition 50 mass% or less is preferable with respect to 100 mass% of non volatile matters in it, 40 mass% or less is more preferable, and 30 mass% or less is still more preferable. Further, from the viewpoint of sufficiently obtaining the effect of blending the hygroscopic metal oxide, the content is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass with respect to 100% by mass of the nonvolatile content in the resin composition. % Or more is more preferable.
＜可塑剤＞
　本発明の樹脂組成物は、更に可塑剤を含有させることにより、樹脂組成物の柔軟性や成形性を向上させることができる。可塑剤としては、特に限定はされないが、室温で液状の材料が好適に用いられる。可塑剤の具体例としては、パラフィン系プロセスオイル、ナフテン系プロセスオイル、流動パラフィン、ポリエチレンワックス、ポリプロピレンワックス、ワセリン等の鉱物油、ヒマシ油、綿実油、菜種油、大豆油、パーム油、ヤシ油、オリーブ油等の植物油、液状ポリブテン、水添液状ポリブテン、液状ポリブタジエン、水添液状ポリブタジエン等の液状ポリαオレフィン類等が挙げられる。本発明に使用する可塑剤としては、液状ポリαオレフィン類が好ましく、特に液状ポリブタジエンが好ましい。また液状ポリαオレフィンとしては接着性の観点から分子量が低いものが好ましく、重量平均分子量で５００～５０００、更には１０００～３０００の範囲のものが好ましい。これら可塑剤は１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。なお、ここで「液状」とは、室温（２５℃）での可塑剤の状態である。本発明の樹脂組成物が可塑剤を含有する場合、樹脂組成物中の不揮発分を１００質量％とした場合、有機ＥＬ素子への悪影響を及ぼさないという観点から、５０質量％以下の範囲内で使用される。 <Plasticizer>
The resin composition of the present invention can improve the flexibility and moldability of the resin composition by further containing a plasticizer. Although it does not specifically limit as a plasticizer, A liquid material is suitably used at room temperature. Specific examples of plasticizers include paraffinic process oil, naphthenic process oil, liquid paraffin, polyethylene wax, polypropylene wax, petroleum jelly and other mineral oils, castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, palm oil, olive oil. And other liquid oils such as vegetable oil, liquid polybutene, hydrogenated liquid polybutene, liquid polybutadiene, and hydrogenated liquid polybutadiene. As the plasticizer used in the present invention, liquid polyα-olefins are preferable, and liquid polybutadiene is particularly preferable. The liquid polyα-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 5000, more preferably 1000 to 3000. These plasticizers may be used alone or in combination of two or more. Here, “liquid” means a state of a plasticizer at room temperature (25 ° C.). When the resin composition of the present invention contains a plasticizer, when the nonvolatile content in the resin composition is 100% by mass, from the viewpoint of not having an adverse effect on the organic EL element, within the range of 50% by mass or less. used.
＜その他の添加剤＞
　本発明の樹脂組成物には、本発明の効果を阻害しない程度に、上述した成分以外の各種添加剤を任意で含有させても良い。このような添加剤としては、例えば、シリカ、硫酸バリウム、タルク、クレー、雲母粉、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、窒化ホウ素、ホウ酸アルミニウム、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、酸化チタン、ジルコン酸バリウム、ジルコン酸カルシウム等の無機充填材；ゴム粒子、シリコーンパウダー、ナイロンパウダー、フッ素樹脂パウダー等の有機充填剤；オルベン、ベントン等の増粘剤；シリコン系、フッ素系、高分子系の消泡剤またはレベリング剤；トリアゾール化合物、チアゾール化合物、トリアジン化合物、ポルフィリン化合物等の密着性付与剤；等を挙げることができる。 <Other additives>
The resin composition of the present invention may optionally contain various additives other than the above-described components to the extent that the effects of the present invention are not impaired. Examples of such additives include silica, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, and strontium titanate. Inorganic fillers such as calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate; organic fillers such as rubber particles, silicone powder, nylon powder, fluororesin powder; Orben, Benton Thickeners such as silicon-based, fluorine-based, polymer-based antifoaming agents or leveling agents; adhesion imparting agents such as triazole compounds, thiazole compounds, triazine compounds, porphyrin compounds; and the like.
　本発明の樹脂組成物の調製方法は、特に限定されるものではなく、配合成分を、必要により溶媒等を添加し、混練ローラーや回転ミキサーなどを用いて混合する方法などが挙げられる。 The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the compounding ingredients are mixed with a kneading roller, a rotary mixer, or the like, if necessary, by adding a solvent or the like.
　本発明の樹脂組成物は、半導体、太陽電池、高輝度ＬＥＤ、ＬＣＤ、ＥＬ素子等の電子部品の封止に使用される。特に有機ＥＬ素子の封止に好適に使用され、具体的には、有機ＥＬ素子の発光部の上部および／または周囲（側部）に適用して有機ＥＬ素子の発光部を外部から保護するために用いることができる。      The resin composition of the present invention is used for sealing electronic parts such as semiconductors, solar cells, high-brightness LEDs, LCDs and EL elements. In particular, it is preferably used for sealing an organic EL element, and specifically, applied to the upper part and / or the periphery (side part) of the light emitting part of the organic EL element to protect the light emitting part of the organic EL element from the outside. Can be used.
　本発明の樹脂組成物を有機ＥＬ素子に適用する場合、樹脂組成物により形成される封止層の透明性は、分光光度計により測定することができる。透明性は有機ＥＬ素子の発光効率を向上させるという点で高いほど良い。具体的には、３０μｍの厚さの封止層において、４５０ｎｍにおける平行線透過率が８０％以上が好ましく、８２％以上がより好ましく、８４％以上が更に好ましく、８６％以上が更に一層好ましく、８８％以上が殊更好ましく、９０％以上が特に好ましい。 When applying the resin composition of the present invention to an organic EL device, the transparency of the sealing layer formed of the resin composition can be measured with a spectrophotometer. The higher the transparency, the better the light emission efficiency of the organic EL element. Specifically, in the sealing layer having a thickness of 30 μm, the parallel line transmittance at 450 nm is preferably 80% or more, more preferably 82% or more, still more preferably 84% or more, and still more preferably 86% or more, 88% or more is particularly preferable, and 90% or more is particularly preferable.
　本発明の樹脂組成物は、（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂の酸無水物基と（Ｂ）エポキシ樹脂のエポキシ基が反応して生じるエステル結合が形成されているのが好ましい。このように架橋構造を形成することで、接着湿熱耐性、耐透湿性等に優れた封止層を形成することができる。エステル結合を形成させるには、例えば、樹脂組成物に有機溶剤を含有させ、ワニス状の樹脂組成物を調製し、該ワニスを加熱乾燥することで形成させることができる。有機溶剤の乾燥は熱風吹きつけ等によって行うことができる。 The resin composition of the present invention comprises (A) an ester bond formed by reacting an acid anhydride group of a polyolefin resin modified with (meth) acrylic acid alkyl ester and an acid anhydride and an epoxy group of (B) an epoxy resin. Is preferably formed. By forming a cross-linked structure in this way, a sealing layer excellent in adhesion moisture heat resistance, moisture permeability resistance, and the like can be formed. In order to form an ester bond, for example, an organic solvent is contained in the resin composition, a varnish-like resin composition is prepared, and the varnish is heated and dried. The organic solvent can be dried by blowing hot air or the like.
　有機溶剤としては、例えば、アセトン、メチルエチルケトン（以下、「ＭＥＫ」とも略称する）、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル類；セロソルブ、ブチルカルビトール等のカルビトール類；トルエン、キシレン等の芳香族炭化水素類；ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等；ソルベントナフサ等の芳香族系混合溶剤を挙げることができる。芳香族系混合溶剤として「スワゾール」（丸善石油社製、商品名）、「イプゾール」（出光興産社製、商品名）が挙げられる。有機溶剤は１種または２種以上組み合わせて使用してもよい。 Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (hereinafter also abbreviated as “MEK”), cyclohexanone; and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like; and aromatic mixed solvents such as solvent naphtha. Examples of aromatic mixed solvents include “Swazole” (trade name, manufactured by Maruzen Petroleum Corporation) and “Ipsol” (trade name, manufactured by Idemitsu Kosan Co., Ltd.). You may use an organic solvent 1 type or in combination of 2 or more types.
　乾燥条件は特に制限はないが、５０～１００℃で１～６０分が好ましい。５０℃以上とすることで、樹脂組成物層中に残存する溶剤量を低下させ易くなる。 Drying conditions are not particularly limited, but preferably 50 to 100 ° C. for 1 to 60 minutes. By setting it as 50 degreeC or more, it becomes easy to reduce the amount of solvent which remains in a resin composition layer.
＜封止用シート＞
　本発明の封止用シートは、支持体上に接着層が形成された封止用シートであり、接着層が本発明の樹脂組成物により形成されたものである。接着層は、例えば、有機溶剤に本発明の樹脂組成物を溶解したワニスを調製し、支持体上に、ワニスを塗布、乾燥することで形成される。有機溶剤の乾燥は熱風吹きつけ等によって行うことができ、この乾燥時に樹脂組成物中の（Ａ）成分の酸無水物基と（Ｂ）成分のエポキシ基が反応して生じるエステル結合が形成されているのが好ましい。このようなエステル結合による架橋構造が形成されることで、樹脂組成物は接着湿熱耐性、耐透湿性等に優れた感圧接着性の樹脂組成物になる。有機溶剤の具体例としては、前記有機溶剤と同様のものを挙げることができ、乾燥条件も前記の乾燥条件と同じ条件を用いることができる。 <Sealing sheet>
The sealing sheet of the present invention is a sealing sheet in which an adhesive layer is formed on a support, and the adhesive layer is formed of the resin composition of the present invention. The adhesive layer is formed, for example, by preparing a varnish obtained by dissolving the resin composition of the present invention in an organic solvent, and applying and drying the varnish on a support. The organic solvent can be dried by blowing hot air or the like. During this drying, an ester bond formed by the reaction of the acid anhydride group of the component (A) and the epoxy group of the component (B) in the resin composition is formed. It is preferable. By forming such a crosslinked structure by an ester bond, the resin composition becomes a pressure-sensitive adhesive resin composition excellent in adhesion moisture heat resistance, moisture permeation resistance, and the like. Specific examples of the organic solvent include those similar to the organic solvent, and the drying conditions can be the same as the drying conditions.
　封止用シートにおける接着層の厚さは、３μｍ～２００μｍが好ましく、５μｍ～１００μｍがより好ましく、５μｍ～５０μｍが更に好ましい。 The thickness of the adhesive layer in the sealing sheet is preferably 3 μm to 200 μm, more preferably 5 μm to 100 μm, and even more preferably 5 μm to 50 μm.
　なお、後述のように、目的とする最終的な封止構造が、接着層（樹脂組成物層）に封止基材が積層された構造の場合、水分が浸入し得る部分は接着層の側部のみになるため、接着層の層厚を薄くすることで、側部の外気と接触する面積が小さくなる。従って、接着層の層厚を薄くすることが、水分を遮断する上で望ましい。しかし、接着層の層厚が小さすぎると、封止基材を貼り合わせる際に素子にダメージを与える虞があり、また、封止基材を貼り合わせる際の作業性が低下する傾向にある。また、接着層の厚みを上記の好適範囲とすることは、封止対象（例えば、有機ＥＬ素子等の素子が形成された基板）に接着層を転写した後の接着層の厚みの均一性を保つ上でも有効である。
　封止用シートに使用する支持体としては、防湿性を有する支持体が好ましい。防湿性を有する支持体としては、防湿性を有するプラスチックフィルムや、銅箔、アルミニウム箔などの金属箔等が挙げられる。防湿性を有するプラスチックフィルムとしては、酸化ケイ素（シリカ）、窒化ケイ素、ＳｉＣＮ、アモルファスシリコン等の無機物を表面に蒸着させたプラスチックフィルム等が挙げられる。ここで、表面に無機物が蒸着されるプラスチックフィルムとしては、例えば、ポリオレフィン（例えば、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等）、ポリエステル（例えば、ポリエチレンテレフタレート（以下「ＰＥＴ」と略称することがある。）、ポリエチレンナフタレート等）、ポリカーボネート、ポリイミド等のプラスチックフィルムが好適であり、ＰＥＴフィルムが特に好ましい。市販されている防湿性を有するプラスチックフィルムの例としては、テックバリアＨＸ、ＡＸ、ＬＸ、Ｌシリーズ（三菱樹脂社製）や、該テックバリアＨＸ、ＡＸ、ＬＸ、Ｌシリーズよりも更に防湿効果を高めたＸ－ＢＡＲＲＩＥＲ（三菱樹脂社製）等が挙げられる。また、防湿性を有する支持体として、２層以上の複層構造を有するもの、例えば、上記のプラスチックフィルムと上記の金属箔とを接着剤を介して張り合わせたものも使用できる。このものは安価であり、ハンドリング性の観点からも有利である。なお、樹脂組成物シートの支持体には、防湿性を有しない支持体（例えば、上記の表面に無機物が蒸着されていないプラスチックフィルムの単体）も使用できる。 As will be described later, when the final sealing structure of interest is a structure in which a sealing substrate is laminated on an adhesive layer (resin composition layer), the portion where moisture can enter is on the side of the adhesive layer. Therefore, by reducing the thickness of the adhesive layer, the area in contact with the outside air on the side portion is reduced. Therefore, it is desirable to reduce the thickness of the adhesive layer in order to block moisture. However, if the layer thickness of the adhesive layer is too small, the element may be damaged when the sealing substrate is bonded, and the workability when the sealing substrate is bonded tends to be lowered. Further, setting the thickness of the adhesive layer within the above preferable range means that the uniformity of the thickness of the adhesive layer after the adhesive layer is transferred to a sealing target (for example, a substrate on which an element such as an organic EL element is formed). It is also effective in maintaining.
As the support used for the sealing sheet, a support having moisture resistance is preferable. Examples of the moisture-proof support include a moisture-proof plastic film, a metal foil such as a copper foil and an aluminum foil, and the like. Examples of the plastic film having moisture resistance include a plastic film in which an inorganic substance such as silicon oxide (silica), silicon nitride, SiCN, amorphous silicon or the like is deposited on the surface. Here, examples of the plastic film on which an inorganic substance is deposited on the surface include, for example, polyolefin (for example, polyethylene, polypropylene, polyvinyl chloride, etc.), polyester (for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”). , Polyethylene naphthalate, etc.), plastic films such as polycarbonate and polyimide are preferred, and PET films are particularly preferred. Examples of commercially available moisture-proof plastic films include the Tech Barrier HX, AX, LX, L series (Mitsubishi Resin Co., Ltd.) and the moisture barrier effect even more than the Tech Barrier HX, AX, LX, L series. X-BARRIER (manufactured by Mitsubishi Plastics), etc. In addition, as the support having moisture resistance, a support having a multilayer structure of two or more layers, for example, a laminate of the above plastic film and the above metal foil with an adhesive may be used. This is inexpensive and advantageous from the viewpoint of handling properties. In addition, the support body which does not have moisture resistance (For example, the single body of the plastic film in which the inorganic substance is not vapor-deposited on the said surface) can also be used for the support body of a resin composition sheet.
　支持体の厚さは特に限定されないが、封止用シートの取り扱い性等の観点から、１０～１５０μｍが好ましく、２０～１００μｍがより好ましい。 The thickness of the support is not particularly limited, but is preferably from 10 to 150 μm, more preferably from 20 to 100 μm, from the viewpoint of the handleability of the sealing sheet.
　また、本発明の封止用シートは実際に封止構造の形成に使用する前までは、接着層（樹脂組成物層）表面へのゴミ等の付着やキズを防止するために接着層表面が保護フィルムで保護されているのが好ましく、保護フィルムとしては、上記の支持体で例示したプラスチックフィルムを用いることができる。保護フィルムは予めマット処理、コロナ処理の他、離型処理を施してあってもよい。離型剤としては、具体的には、フッ素系離型剤、シリコーン系離型剤、アルキッド樹脂系離型剤等が挙げられる。離型剤は異なる種類のものを混合して用いてもよい。保護フィルムの厚さも特に制限されないが、１～４０μｍが好ましく、１０～３０μｍがより好ましい。 In addition, the surface of the adhesive layer of the present invention has a surface to prevent dust from adhering to the surface of the adhesive layer (resin composition layer) and scratches until it is actually used for forming a sealing structure. The protective film is preferably protected, and as the protective film, the plastic film exemplified in the above support can be used. The protective film may be subjected to a mold release treatment in addition to a mat treatment and a corona treatment. Specific examples of the release agent include a fluorine-based release agent, a silicone-based release agent, and an alkyd resin-based release agent. Different types of release agents may be mixed and used. The thickness of the protective film is not particularly limited, but is preferably 1 to 40 μm, and more preferably 10 to 30 μm.
　本発明の封止用シートは、封止対象にラミネートして使用される。ここでいう、「ラミネート」は支持体を備えたままの封止用シートで封止対象が被覆された状態の他、封止対象が封止用シートから転写された接着層（樹脂組成物層）で被覆された状態を含む。支持体が防湿性を有しない支持体（例えば、上記の表面に無機物が蒸着されていないプラスチックフィルムの単体）である封止用シートを使用する場合、封止対象に封止用シートをラミネートした後、支持体を剥離し（すなわち、接着層（樹脂組成物層）を転写し）、その後、接着層上に、別途、封止基材を積層するのが好ましい。特に、封止対象が有機ＥＬ素子が形成された基板（以下、「有機ＥＬ素子形成基板」ともいう）である場合、かかる封止基材を積層する態様が好ましい。なお、本発明でいう「封止基材」は、封止用シートに用いた防湿性を有する支持体を、それに接着層（樹脂組成物層）を形成せずに、それ単体で使用するものである。また、封止用シートの支持体として使用するには不向きな、ガラス板、金属板、鋼板等の可とう性を有しないが、防湿性の高い板も「封止基材」に含まれる。 The sealing sheet of the present invention is used by being laminated on a sealing target. As used herein, “laminate” refers to an adhesive layer (resin composition layer) in which the object to be sealed is covered with a sealing sheet with a support, and the object to be sealed is transferred from the sheet for sealing. ) Covered. When using a sealing sheet that is a support that does not have moisture resistance (for example, a single plastic film with no inorganic material deposited on the surface), the sealing sheet is laminated to the object to be sealed. After that, it is preferable to peel the support (that is, transfer the adhesive layer (resin composition layer)), and then separately laminate a sealing substrate on the adhesive layer. In particular, when the sealing target is a substrate on which an organic EL element is formed (hereinafter, also referred to as “organic EL element forming substrate”), a mode in which such sealing substrates are laminated is preferable. In addition, the “sealing substrate” as used in the present invention is the one that uses the moisture-proof support used for the sealing sheet alone without forming an adhesive layer (resin composition layer) on it. It is. In addition, a “sealing substrate” also includes a highly moisture-proof plate that does not have flexibility such as a glass plate, a metal plate, and a steel plate, which is unsuitable for use as a support for a sealing sheet.
＜有機ＥＬデバイス＞
　本発明の有機ＥＬデバイスは、有機ＥＬ素子が封止層により封止されている有機ＥＬデバイスであり、封止層が本願の樹脂組成物により形成されているものである。たとえば、有機ＥＬ素子を有する基板に本発明の封止用シートをラミネートすることで、本発明の有機ＥＬデバイスが得られる。封止用シートが保護フィルムで保護されている場合はこれを剥離した後、接着層（樹脂組成物層）が有機ＥＬ素子を有する基板に直接接するように、封止用シートを該有機ＥＬ素子を有する基板上にラミネートする。ラミネートの方法はバッチ式であってもロールでの連続式であってもよい。 <Organic EL device>
The organic EL device of the present invention is an organic EL device in which an organic EL element is sealed with a sealing layer, and the sealing layer is formed of the resin composition of the present application. For example, the organic EL device of the present invention can be obtained by laminating the sealing sheet of the present invention on a substrate having an organic EL element. When the sealing sheet is protected by a protective film, the organic EL element is removed from the sealing sheet so that the adhesive layer (resin composition layer) is in direct contact with the substrate having the organic EL element. Is laminated on a substrate having The laminating method may be a batch method or a continuous method using a roll.
　封止用シートの支持体が防湿性を有する支持体である場合は、封止用シートを有機ＥＬ素子を有する基板上にラミネートした後、支持体を剥離せず、そのまま有機ＥＬ素子の封止工程が完了する。封止工程後に熱硬化が必要な場合は、熱硬化を行う。こうすることで、有機ＥＬ素子が本発明の樹脂組成物により形成された封止層により封止された有機ＥＬデバイスが得られる。 When the support of the sealing sheet is a moisture-proof support, after sealing the sealing sheet on the substrate having the organic EL element, the support is not peeled off and the organic EL element is sealed as it is. The process is complete. When thermosetting is necessary after the sealing step, thermosetting is performed. By carrying out like this, the organic EL device by which the organic EL element was sealed with the sealing layer formed with the resin composition of this invention is obtained.
　一般的に、有機ＥＬ素子の封止用材料は、封止作業の前に乾燥させて、吸水した水分を除去することが必要であり、その作業が煩雑であるが、防湿性を有する支持体を使用した本発明の封止用シートは耐透湿性が高いため、保存時やデバイス製造作業時における吸水率も低い。また、封止作業時の有機ＥＬ素子に与えるダメージも著しく軽減される。 In general, a sealing material for an organic EL element needs to be dried before sealing work to remove the absorbed water, and the work is complicated, but the support has moisture resistance. Since the sealing sheet of the present invention using a high moisture permeation resistance, the water absorption rate during storage and device manufacturing operations is also low. Moreover, the damage given to the organic EL element at the time of sealing work is also remarkably reduced.
　防湿性を有しない支持体を使用した封止用シートを使用する場合、有機ＥＬ素子を有する基板に封止用シートをラミネート後、支持体を剥離し、露出した接着層（樹脂組成物層）に封止基材を圧着することで、有機ＥＬ素子の封止工程が完了する。封止基材は、防湿効果が上がるという観点から、２枚またはそれ以上を貼り合わせて使用してもよい。また、封止基材の厚みは有機ＥＬデバイス自体を薄くかつ軽くするという観点から５ｍｍ以下が好ましく、１ｍｍ以下がより好ましく、１００μｍ以下が更に好ましくい。また、水分透過を防ぐ観点から、５μｍ以上が好ましく、１０μｍ以上がより好ましく、２０μｍ以上が更に好ましい。封止基材の圧着時の圧力は０．３～１０ｋｇｆ／ｃｍ２程度が好適であり、加熱下に圧着する場合、２５℃～１３０℃が好適である。 When a sealing sheet using a support that does not have moisture resistance is used, the support sheet is peeled off after laminating the sealing sheet on a substrate having an organic EL element, and an exposed adhesive layer (resin composition layer) The sealing process of the organic EL element is completed by pressure-bonding the sealing substrate to the substrate. Two or more sealing substrates may be used by bonding them from the viewpoint of improving the moisture-proof effect. Further, the thickness of the sealing substrate is preferably 5 mm or less, more preferably 1 mm or less, and further preferably 100 μm or less from the viewpoint of making the organic EL device itself thin and light. From the viewpoint of preventing moisture permeation, it is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 20 μm or more. The pressure at the time of press-bonding the sealing substrate is preferably about 0.3 to 10 kgf / cm 2 , and 25 to 130 ° C. is preferable when the pressure is applied under heating.
　有機ＥＬ素子を有する基板が透明基板上に有機ＥＬ素子が形成されたものである場合、透明基板側をディスプレイの表示面や照明器具の発光面にすれば、封止用シートの支持体には必ずしも透明材料を使用する必要はなく、金属板、金属箔、不透明のプラスチックフィルムまたは板等を使用してもよい。逆に有機ＥＬ素子を有する基板が有機ＥＬ素子が不透明または透明性の低い材料からなる基板上に形成されたものである場合、封止基材側をディスプレイの表示面や照明器具の発光面にする必要から、封止基材には、透明プラスチックフィルム、ガラス板、透明プラスチック板等が使用される。 When the substrate having an organic EL element is an organic EL element formed on a transparent substrate, if the transparent substrate side is a display surface of a display or a light emitting surface of a lighting fixture, It is not always necessary to use a transparent material, and a metal plate, metal foil, opaque plastic film, or plate may be used. On the contrary, when the substrate having the organic EL element is formed on a substrate made of an opaque or low-transparency material, the sealing substrate side is used as the display surface of the display or the light emitting surface of the lighting fixture. Therefore, a transparent plastic film, a glass plate, a transparent plastic plate or the like is used as the sealing substrate.
　以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の記載において、特に断りがない限り、「部」は「質量部」、「％」は「質量％」を意味する。 Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. In the following description, “parts” means “parts by mass” and “%” means “% by mass” unless otherwise specified.
　まず、実施例および比較例に用いた使用材料について説明する。
（Ａ）変性ポリオレフィン系樹脂
　・Ｔ－ＹＰ４２９（星光ＰＭＣ社製）：アクリル酸２－エチルヘキシルおよび無水マレイン酸変性エチレン－メチルメタクリレート共重合体（エチレン単位／メチルメタクリレート単位＝６８質量％／３２質量％、無水マレイン酸基濃度０．４６mmol／ｇ、変性共重合体の数平均分子量２３００、グラフト鎖の数平均分子量３８６、グラフト鎖中のアクリル酸２－エチルヘキシル単位の含有量５０質量％）
　・Ｔ－ＹＰ４３０（星光ＰＭＣ社製）：アクリル酸２－エチルヘキシルおよび無水マレイン酸変性エチレン－メチルメタクリレート共重合体（エチレン単位／メチルメタクリレート単位＝６８質量％／３２質量％、無水マレイン酸基濃度１．１８mmol／ｇ、変性共重合体の数平均分子量４５００、グラフト鎖の数平均分子量３８６、グラフト鎖中のアクリル酸２－エチルヘキシル単位の含有量５０質量％）
　・Ｔ－ＹＰ９５３（星光ＰＭＣ社製）：アクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－ブテン共重合体８０質量％とアクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－エチレン共重合体２０質量％の混合物（無水マレイン酸基濃度０．４４mmol／ｇ、変性共重合体の数平均分子量３３２００、グラフト鎖の数平均分子量８５６、グラフト鎖中のアクリル酸２－エチルヘキシル単位の含有量５０質量％）
　・Ｔ－ＹＰ９５５（星光ＰＭＣ社製）：アクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－ブテン共重合体質量６７％とアクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－エチレン共重合体３３質量％の混合物（無水マレイン酸基濃度０．９４mmol／ｇ、変性共重合体の数平均分子量２２７００、グラフト鎖の数平均分子量６２０、グラフト鎖中のアクリル酸２－エチルヘキシル単位の含有量５０質量％）
　・Ｔ－ＹＰ９５６（星光ＰＭＣ社製）：アクリル酸２－エチルヘキシルおよび無水マレイン酸変性エチレン－プロピレン－ブテンランダム共重合体（無水マレイン酸基濃度１．８０mmol／ｇ、変性共重合体の数平均分子量３０００、グラフト鎖の数平均分子量４２３、グラフト鎖中のアクリル酸２－エチルヘキシル単位の含有量５０質量％）
　・Ｔ－ＹＰ２７９（星光ＰＭＣ社製）：アクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－ブテンランダム共重合体（プロピレン単位／ブテン単位＝６４質量％／３６質量％、無水マレイン酸基濃度０．４６４mmol／ｇ、数平均分子量３５０００グラフト鎖の数平均分子量６４４、グラフト鎖中のアクリル酸２－エチルヘキシル単位の含有量５０質量％）
　・Ｔ－ＹＰ３１２（星光ＰＭＣ社製）：アクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－ブテン共重合体（プロピレン単位／ブテン単位＝７１質量％／２９質量％、無水マレイン酸基濃度０．４６４mmol／ｇ、変性共重合体の数平均分子量６０９００、グラフト鎖の数平均分子量６１１、グラフト鎖中のアクリル酸２－エチルヘキシル単位の含有量５０質量％）（Ｂ）エポキシ樹脂
　・８２８ＥＬ（三菱化学社製）：ビスフェノールＡ型エポキシ樹脂、エポキシ当量１９０ｇ／ｅｑ
　・ＥＰＩＣＬＯＮ ＥＸＡ４８５０－１０００（ＤＩＣ社製）：ポリプロピレングリコール骨格含有エポキシ樹脂、エポキシ当量３５０ｇ／ｅｑ
　・Ｔ－ＹＰ４３１（星光ＰＭＣ社製）：グリシジルメタクリレート変性エチレン－メチルメタクリレート共重合体（エポキシ基濃度０．６４mmol/g、数平均分子量２４００）
　・Ｔ－ＹＰ４３２（星光ＰＭＣ社製）：グリシジルメタクリレート変性エチレン－メチルメタクリレート共重合体（エポキシ基濃度１．６３mmol/g、数平均分子量３１００）
　・ＢＯＮＤＦＡＳＴ ＢＦ-７Ｍ（住友化学社製）：エチレン－グリシジルメタクリレート共重合体（エポキシ基濃度０．４mmol/g）
　・Ｔ－ＹＰ２５２（星光ＰＭＣ社製）：グリシジルメタクリレート変性プロピレン－ブランダム共重合体８０％とグリシジルメタクリレート変性プロピレン－エチレンランダム共重合体２０％の混合物（エポキシ基濃度０．６４mmol／ｇ、数平均分子量３４０００）
　・Ｔ－ＹＰ３１３（星光ＰＭＣ社製）：グリシジルメタクリレート変性プロピレン－ブテンランダム共重合体（プロピレン単位／ブテン単位＝７１質量％／２９質量％、エポキシ基濃度０．６３８mmol／ｇ、数平均分子量１５５０００）
　・Ｔ－ＹＰ２７６（星光ＰＭＣ社製）：グリシジルメタクリレート変性プロピレン－ブテンランダム共重合体（プロピレン単位／ブテン単位＝６４質量％／２９質量％、エポキシ基濃度０．６３８mmol/g、数平均分子量５７０００）
（Ｃ）粘着付与樹脂
　・ＴＦＳ１３－０３０（荒川化学社製）：シクロヘキサン環含有飽和炭化水素樹脂、軟化点１２５℃
（Ｄ）硬化促進剤
　・アニオン重合型硬化促進剤：２，４，６－トリス（ジメチルアミノメチル）フェノール（以下「ＴＡＰ」と略記）
（Ｆ）吸湿性金属酸化物
　・焼成ハイドロタルサイト（協和化学工業製「ＤＨＴ－４Ｃ」）
（その他の材料）
　・ＡＣＲＹＦＴ　ＣＭ５０２２（住友化学（株）製）：エチレン－メチルメタクリレート共重合体
　・Ｌ－ＭＯＤＵ　Ｓ４００（出光興産社製）：ポリプロプレン樹脂、平均分子量４５０００
　・ＳＩＢＳＴＡＲ－１０２Ｔ（カネカ社製）：スチレン－イソブチレン－スチレンブロック共重合体、平均分子量１０００００
　・スワゾール＃１０００（丸善石油社製）：芳香族系混合溶剤
　・トルエン First, materials used in Examples and Comparative Examples will be described.
(A) Modified polyolefin-based resin T-YP429 (manufactured by Seiko PMC): 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer (ethylene unit / methyl methacrylate unit = 68% by mass / 32% by mass) The maleic anhydride group concentration 0.46 mmol / g, the number average molecular weight 2300 of the modified copolymer, the number average molecular weight 386 of the graft chain, the content of 2-ethylhexyl acrylate units in the graft chain of 50% by mass)
T-YP430 (manufactured by Seiko PMC): 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer (ethylene unit / methyl methacrylate unit = 68% by mass / 32% by mass, maleic anhydride group concentration 1) .18 mmol / g, number average molecular weight of modified copolymer 4500, number average molecular weight of graft chain 386, content of 2-ethylhexyl acrylate unit in graft chain 50% by mass)
T-YP953 (manufactured by Seiko PMC): 80% by mass of 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer and 20% by mass of 2-ethylhexyl acrylate and maleic anhydride modified propylene-ethylene copolymer (Maleic anhydride group concentration 0.44 mmol / g, modified copolymer number average molecular weight 33200, graft chain number average molecular weight 856, content of 2-ethylhexyl acrylate units in the graft chain 50% by mass)
T-YP955 (manufactured by Seiko PMC): 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer mass 67% and 2-ethylhexyl acrylate and maleic anhydride modified propylene-ethylene copolymer 33 mass% (Maleic anhydride group concentration 0.94 mmol / g, modified copolymer number average molecular weight 22700, graft chain number average molecular weight 620, content of 2-ethylhexyl acrylate units in the graft chain 50 mass%)
T-YP956 (manufactured by Seiko PMC): 2-ethylhexyl acrylate and maleic anhydride modified ethylene-propylene-butene random copolymer (maleic anhydride group concentration 1.80 mmol / g, number average molecular weight of modified copolymer) 3000, number average molecular weight of graft chain 423, content of 2-ethylhexyl acrylate unit in graft chain 50% by mass)
T-YP279 (manufactured by Seiko PMC): 2-ethylhexyl acrylate and maleic anhydride-modified propylene-butene random copolymer (propylene unit / butene unit = 64% by mass / 36% by mass, maleic anhydride group concentration 0. 464 mmol / g, number average molecular weight 35,000 number average molecular weight of graft chain 644, content of 2-ethylhexyl acrylate unit in graft chain 50% by mass)
T-YP312 (manufactured by Seiko PMC): 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (propylene unit / butene unit = 71 mass% / 29 mass%, maleic anhydride group concentration 0.464 mmol) / G, number average molecular weight 60900 of the modified copolymer, number average molecular weight 611 of the graft chain, content of 2-ethylhexyl acrylate unit in the graft chain 50% by mass) (B) epoxy resin 828EL (manufactured by Mitsubishi Chemical Corporation) ): Bisphenol A type epoxy resin, epoxy equivalent 190 g / eq
EPICLON EXA4850-1000 (manufactured by DIC): epoxy resin containing polypropylene glycol skeleton, epoxy equivalent 350 g / eq
T-YP431 (manufactured by Seiko PMC): Glycidyl methacrylate modified ethylene-methyl methacrylate copolymer (epoxy group concentration 0.64 mmol / g, number average molecular weight 2400)
T-YP432 (manufactured by Seiko PMC): glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (epoxy group concentration 1.63 mmol / g, number average molecular weight 3100)
BONDFAST BF-7M (manufactured by Sumitomo Chemical): ethylene-glycidyl methacrylate copolymer (epoxy group concentration 0.4 mmol / g)
T-YP252 (manufactured by Seiko PMC): A mixture of 80% glycidyl methacrylate-modified propylene-brandum copolymer and 20% glycidyl methacrylate-modified propylene-ethylene random copolymer (epoxy group concentration 0.64 mmol / g, number average molecular weight) 34000)
T-YP313 (manufactured by Seiko PMC): glycidyl methacrylate-modified propylene-butene random copolymer (propylene unit / butene unit = 71% by mass / 29% by mass, epoxy group concentration 0.638 mmol / g, number average molecular weight 155000)
T-YP276 (manufactured by Seiko PMC): glycidyl methacrylate-modified propylene-butene random copolymer (propylene unit / butene unit = 64 mass% / 29 mass%, epoxy group concentration 0.638 mmol / g, number average molecular weight 57000)
(C) Tackifying resin TFS13-030 (Arakawa Chemical Co., Ltd.): Cyclohexane ring-containing saturated hydrocarbon resin, softening point 125 ° C
(D) Curing accelerator Anionic polymerization type curing accelerator: 2,4,6-tris (dimethylaminomethyl) phenol (hereinafter abbreviated as “TAP”)
(F) Hygroscopic metal oxides ・ Firing hydrotalcite (“DHT-4C” manufactured by Kyowa Chemical Industry)
(Other materials)
ACRYFT CM5022 (manufactured by Sumitomo Chemical Co., Ltd.): ethylene-methyl methacrylate copolymer L-MODU S400 (manufactured by Idemitsu Kosan Co., Ltd.): Polypropylene resin, average molecular weight 45000
SIBSTAR-102T (manufactured by Kaneka): styrene-isobutylene-styrene block copolymer, average molecular weight 100,000
・ Swazole # 1000 (manufactured by Maruzen Petroleum Corporation): Aromatic mixed solvent ・ Toluene
［測定方法・評価方法］
 各種測定方法・評価方法について説明する。 [Measurement and evaluation methods]
Various measurement methods and evaluation methods will be described.
＜接着湿熱耐性の評価＞
　支持体にＰＥＴフィルムを使用した封止用シート（長さ５０ｍｍ、幅２０ｍｍ）をバッチ式真空ラミネーター（ニチゴー・モートン社製、Ｍｏｒｔｏｎ－７２４）を用いて、アルミニウム箔（長さ１００ｍｍ、幅２０ｍｍ、厚さ５０μｍ、住軽アルミ箔社製、品番ＳＡ５０）にラミネートした。ラミネートは、温度８０℃、時間３００秒、圧力０．３ＭＰaの条件で行った。そしてＰＥＴフィルムを剥離し、露出した樹脂組成物層上に、さらにガラス板（長さ７６ｍｍ、幅２６ｍｍ、厚さ１．２ｍｍ、マイクロスライドガラス）を上記と同じ条件でラミネートした。得られた積層体について、アルミニウム箔の長さ方向に対して、９０度方向に、引張り速度を５０ｍｍ／分として剥離したときの接着強度を測定した（初期接着強度）。また、上記と同様にして作製した試験片を８５℃、８５％ＲＨの条件下で２４時間保持した後に、上記の方法で接着強度を測定した（高温高湿環境試験後の接着強度）。 <Evaluation of adhesive heat resistance>
Using a batch type vacuum laminator (manufactured by Nichigo Morton, Morton-724), an aluminum foil (length: 100 mm, width: 20 mm) was prepared by using a sealing sheet (length: 50 mm, width: 20 mm) using a PET film as a support. It was laminated to a thickness of 50 μm, manufactured by Sumi Light Aluminum Foil Co., Ltd., product number SA50). Lamination was performed under the conditions of a temperature of 80 ° C., a time of 300 seconds, and a pressure of 0.3 MPa. The PET film was peeled off, and a glass plate (length 76 mm, width 26 mm, thickness 1.2 mm, micro slide glass) was further laminated on the exposed resin composition layer under the same conditions as described above. About the obtained laminated body, the adhesive strength when it peeled by 90-degree direction with respect to the length direction of aluminum foil and making a tension | pulling speed 50mm / min was measured (initial adhesive strength). Moreover, after holding the test piece produced similarly to the above on 85 degreeC and 85% RH conditions for 24 hours, adhesive strength was measured by said method (adhesion strength after a high temperature, high humidity environment test).
＜加工性の評価＞
　樹脂組成物ワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布する際に、ワニスの流動性の持続性（経時安定性）が良好で安定した塗工が可能である場合を○、増粘等により安定した塗工が不可な場合を×と評価した。 <Evaluation of workability>
When the resin composition varnish is uniformly applied by a die coater on the release treated surface of a PET film (thickness 30 μm) treated with a silicone mold release agent, the fluidity of the varnish is sustained (stable over time) Property) was good and stable coating was possible, and the case where stable coating was impossible due to thickening was evaluated as x.
＜耐透湿性の評価＞
　実施例及び比較例で作製した樹脂組成物シートの樹脂組成物層（厚み：４５μｍ）を支持体（ＰＥＴフィルム）から剥離した粘着層に対し、ＪＩＳＺ０２０８に準拠する方法にて、温度４０℃、湿度９０％ＲＨ、２４時間の条件にて、水蒸気透過量を測定し、１ｍ２あたりの水蒸気透過量を求めた。水蒸気透過量が１００ｇ／ｍ２・２４ｈｒ以上の場合は耐透湿性は不良「×」と判定し、１００ｇ／ｍ２・２４ｈｒ未満の場合を良好「○」とした。 <Evaluation of moisture permeability>
With respect to the pressure-sensitive adhesive layer obtained by peeling the resin composition layer (thickness: 45 μm) of the resin composition sheet prepared in Examples and Comparative Examples from the support (PET film), the method according to JISZ0208, temperature 40 ° C., humidity The amount of water vapor transmission per 1 m 2 was determined by measuring the amount of water vapor transmission under the conditions of 90% RH and 24 hours. If the water vapor permeation amount of more than 100g / m 2 · 24hr moisture permeability resistance is determined to be defective "×", and a case of less than 100g / m 2 · 24hr as good "○".
　以下に記載する方法で封止用シートを得た。なお、特に記載のない限り、各部の値は不揮発分で換算した値である。 A sealing sheet was obtained by the method described below. Unless otherwise specified, the value of each part is a value converted in terms of nonvolatile content.
＜実施例１＞
　アクリル酸２－エチルヘキシルおよび無水マレイン酸変性エチレン－メチルメタクリレート共重合体（Ｔ－ＹＰ４２９、２０％トルエン溶液）３７部に、シクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）３５部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にグリシジルメタクリレート変性エチレン－メチメタクリレート共重合体（Ｔ－ＹＰ４３１、２０％トルエン溶液）２７部と、アニオン重合型硬化促進剤（ＴＡＰ）０．５部とを高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Example 1>
To 37 parts of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer (T-YP429, 20% toluene solution), purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) 35 parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 27 parts of a glycidyl methacrylate-modified ethylene-methacrylate copolymer (T-YP431, 20% toluene solution) and 0.5 part of an anionic polymerization accelerator (TAP) are uniformly mixed with a high-speed rotating mixer. And the varnish was obtained. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜実施例２＞
　アクリル酸２－エチルヘキシルおよび無水マレイン酸変性エチレン－メチルメタクリレート共重合体（Ｔ－ＹＰ４３０、２０％トルエン溶液）３７部に、シクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）３５部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にグリシジルメタクリレート変性エチレン－メチルメタクリレート共重合体（Ｔ－ＹＰ４３２、２０％トルエン溶液）２７部と、アニオン重合型硬化促進剤（ＴＡＰ）０．５部とを高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Example 2>
To 37 parts of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer (T-YP430, 20% toluene solution), purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) 35 parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 27 parts of a glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (T-YP432, 20% toluene solution) and 0.5 part of an anionic polymerization accelerator (TAP) are uniformly mixed with a high-speed rotating mixer. And the varnish was obtained. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜実施例３＞
　アクリル酸２－エチルヘキシルおよび無水マレイン酸変性エチレン－メチルメタクリレート共重合体（Ｔ－ＹＰ４２９、２０％スワゾール溶液）３０部に、シクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）３５部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にエチレン－グリシジルメタクリレート共重合体（ＢＯＮＤＦＡＳＴ ＢＦ－７Ｍ 、２０％スワゾール溶液）３４部と、アニオン重合型硬化促進剤（ＴＡＰ）０．５部とを高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Example 3>
30 parts of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-methyl methacrylate copolymer (T-YP429, 20% swazole solution), purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) 35 parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 34 parts of an ethylene-glycidyl methacrylate copolymer (BONDAST BF-7M, 20% swazole solution) and 0.5 part of an anionic polymerization accelerator (TAP) were uniformly mixed with a high-speed rotary mixer. A varnish was obtained. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜実施例４＞
　アクリル酸２－エチルヘキシルおよび無水マレイン酸変性エチレン－プロピレン共重合体とアクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－ブテン共重合体の混合物（Ｔ－ＹＰ９５３、３０％メチルシクロヘキサン＋酢酸ブチル溶液）３７部に、シクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）３６部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にグリシジルメタクリレート変性エチレン－プロピレン共重合体とグリシジルメタクリレート変性プロピレン－ブテン共重合体の混合物（Ｔ－ＹＰ２５２、３０％メチルシクロヘキサン＋酢酸ブチル溶液）２６部と、アニオン重合型硬化促進剤（ＴＡＰ）０．５部とを高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Example 4>
Mixture of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-propylene copolymer and 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP953, 30% methylcyclohexane + butyl acetate solution) 37 36 parts of a cyclohexane ring-containing saturated hydrocarbon resin purified product (TFS13-030, 60% toluene solution) was mixed with a high-speed rotary mixer to obtain a uniform mixed solution. In this mixed solution, 26 parts of a mixture of a glycidyl methacrylate-modified ethylene-propylene copolymer and a glycidyl methacrylate-modified propylene-butene copolymer (T-YP252, 30% methylcyclohexane + butyl acetate solution) and an anionic polymerization type curing accelerator ( TAP) 0.5 part was uniformly mixed with a high-speed rotary mixer to obtain a varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜実施例５＞
　アクリル酸２－エチルヘキシルおよび無水マレイン酸変性エチレン－プロピレン共重合体とアクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－ブテン共重合体の混合物（Ｔ－ＹＰ９５５、３０％メチルシクロヘキサン＋酢酸ブチル溶液）２５部に、シクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）３６部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にグリシジルメタクリレート変性エチレン－プロピレン共重合体とグリシジルメタクリレート変性プロピレン－ブテン共重合体の混合物（Ｔ－ＹＰ２５２、３０％メチルシクロヘキサン＋酢酸ブチル溶液）３８部と、アニオン重合型硬化促進剤（ＴＡＰ）０．５部とを高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Example 5>
Mixture of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-propylene copolymer and 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP955, 30% methylcyclohexane + butyl acetate solution) 25 36 parts of a cyclohexane ring-containing saturated hydrocarbon resin purified product (TFS13-030, 60% toluene solution) was mixed with a high-speed rotary mixer to obtain a uniform mixed solution. In this mixed solution, 38 parts of a mixture of glycidyl methacrylate-modified ethylene-propylene copolymer and glycidyl methacrylate-modified propylene-butene copolymer (T-YP252, 30% methylcyclohexane + butyl acetate solution) and an anionic polymerization type curing accelerator ( TAP) 0.5 part was uniformly mixed with a high-speed rotary mixer to obtain a varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜実施例６＞
　アクリル酸２－エチルヘキシルおよび無水マレイン酸変性エチレン－プロピレン－ブテンランダム共重合体（Ｔ－ＹＰ９５６、５０％メチルシクロヘキサン＋酢酸ブチル溶液）１６部に、シクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）３６部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にグリシジルメタクリレート変性エチレン－プロピレン共重合体とグリシジルメタクリレート変性プロピレン－ブテン共重合体の混合物（Ｔ－ＹＰ２５２、３０％メチルシクロヘキサン＋酢酸ブチル溶液）４７部と、アニオン重合型硬化促進剤（ＴＡＰ）０．５部とを高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Example 6>
To 16 parts of 2-ethylhexyl acrylate and maleic anhydride modified ethylene-propylene-butene random copolymer (T-YP956, 50% methylcyclohexane + butyl acetate solution) purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030) , 60% toluene solution) was mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. In this mixed solution, 47 parts of a mixture of glycidyl methacrylate-modified ethylene-propylene copolymer and glycidyl methacrylate-modified propylene-butene copolymer (T-YP252, 30% methylcyclohexane + butyl acetate solution) and an anionic polymerization type curing accelerator ( TAP) 0.5 part was uniformly mixed with a high-speed rotary mixer to obtain a varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜実施例７＞
　アクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－ブテン共重合体（Ｔ－ＹＰ２７９、４０％スワゾール溶液）２８部に、シクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）５０部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にグリシジルメタクリレート変性プロピレン－ブテン共重合体（Ｔ－ＹＰ２７６、４０％スワゾール溶液）２１部と、アニオン重合型硬化促進剤（ＴＡＰ）０．５部とを高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Example 7>
50 parts of 2-ethylhexyl acrylate and maleic anhydride-modified propylene-butene copolymer (T-YP279, 40% swazole solution) and 50% purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) The parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 21 parts of a glycidyl methacrylate-modified propylene-butene copolymer (T-YP276, 40% swazole solution) and 0.5 part of an anionic polymerization accelerator (TAP) are uniformly mixed with a high-speed rotary mixer. And got the varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜実施例８＞
　アクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－ブテン共重合体（Ｔ－ＹＰ２７９、４０％スワゾール溶液）３５部に、シクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）５０部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にビスフェノールＡ型エポキシ樹脂（８２８ＥＬ）２部と、アニオン重合型硬化促進剤（ＴＡＰ）０．５部とを高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Example 8>
50 parts of cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) is added to 35 parts of 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP279, 40% swazole solution). The parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 2 parts of bisphenol A type epoxy resin (828EL) and 0.5 part of an anionic polymerization accelerator (TAP) were uniformly mixed with a high-speed rotary mixer to obtain a varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜実施例９＞
　アクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－ブテン共重合体（Ｔ－ＹＰ２７９、４０％スワゾール溶液）３５部に、シクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）５０部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にポリプロピレングリコール骨格含有エポキシ樹脂（ＥＰＩＣＬＯＮ ＥＸＡ４８５０－１０００）２部と、アニオン重合型硬化促進剤（ＴＡＰ）０．５部とを高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Example 9>
50 parts of cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution) is added to 35 parts of 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP279, 40% swazole solution). The parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 2 parts of an epoxy resin containing polypropylene glycol skeleton (EPICLON EXA4850-1000) and 0.5 part of an anionic polymerization accelerator (TAP) were uniformly mixed with a high-speed rotary mixer to obtain a varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜実施例１０＞
　アクリル酸２－エチルヘキシルおよび無水マレイン酸変性プロピレン－ブテン共重合体（Ｔ－ＹＰ２７９、４０％スワゾール溶液）２０部と焼成ハイドロタルサイト１４部を混合し３本ロールで混練した後、シクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）５０部を高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にグリシジルメタクリレート変性プロピレン－ブテン共重合体（Ｔ－ＹＰ２７６、４０％スワゾール溶液）１４部と、アニオン重合型硬化促進剤（ＴＡＰ）０．５部とを高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Example 10>
20 parts of 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP279, 40% swazole solution) and 14 parts of calcined hydrotalcite were mixed and kneaded with three rolls, and then cyclohexane ring-containing saturated 50 parts of purified hydrocarbon resin (TFS13-030, 60% toluene solution) was mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 14 parts of a glycidyl methacrylate-modified propylene-butene copolymer (T-YP276, 40% swazole solution) and 0.5 part of an anionic polymerization accelerator (TAP) were uniformly mixed with a high-speed rotating mixer. And got the varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜実施例１１＞
　アクリル酸－２－エチルヘキシルおよび無水マレイン酸変性プロピレン－ブテン共重合体（Ｔ－ＹＰ３１２、４０％スワゾール溶液）２８部に、シクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）５０部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にグリシジルメタクリレート変性プロピレン－ブテン共重合体（Ｔ－ＹＰ３１３、４０％スワゾール溶液）２１部と、アニオン重合型硬化促進剤（ＴＡＰ）０．５部とを高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Example 11>
28 parts of 2-ethylhexyl acrylate and maleic anhydride modified propylene-butene copolymer (T-YP312, 40% swazole solution) and purified hydrocarbon resin containing cyclohexane ring (TFS13-030, 60% toluene solution) 50 parts were mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. To this mixed solution, 21 parts of a glycidyl methacrylate-modified propylene-butene copolymer (T-YP313, 40% swazole solution) and 0.5 part of an anionic polymerization accelerator (TAP) were uniformly mixed with a high-speed rotary mixer. And got the varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜比較例１＞
　ポリプロピレン樹脂（Ｌ－ＭＯＤＵ Ｓ４００、４５％スワゾール溶液）５０部とシクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）５０部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にアニオン重合型硬化促進剤（ＴＡＰ）０．５部を高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Comparative Example 1>
Mix 50 parts polypropylene resin (L-MODU S400, 45% swazole solution) and 50 parts purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution), and mix evenly with a high-speed rotary mixer. A solution was obtained. To this mixed solution, 0.5 part of an anionic polymerization accelerator (TAP) was uniformly mixed with a high-speed rotary mixer to obtain a varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
＜比較例２＞
　スチレン－イソブチレン－スチレンブロック共重合体（ＳＩＢＳＴＡＲ－１０２Ｔ、４５％スワゾール溶液）５０部とシクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）５０部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にアニオン重合型硬化促進剤（ＴＡＰ）０．５部を高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの樹脂組成物シートを得た。 <Comparative example 2>
Mix 50 parts of styrene-isobutylene-styrene block copolymer (SIBSTAR-102T, 45% swazole solution) and 50 parts of purified cyclohexane ring-containing saturated hydrocarbon resin (TFS13-030, 60% toluene solution). To obtain a homogeneous mixed solution. To this mixed solution, 0.5 part of an anionic polymerization accelerator (TAP) was uniformly mixed with a high-speed rotary mixer to obtain a varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A resin composition sheet having a composition layer thickness of 20 μm was obtained.
＜比較例３＞
　ポリエチレン樹脂（ＡＣＲＹＦＴ　ＣＭ５０２２、２０％トルエン溶液）６４部とシクロヘキサン環含有飽和炭化水素樹脂精製物（ＴＦＳ１３－０３０、６０％トルエン溶液）３５部を混合し、高速回転ミキサーで混合して均一混合溶液を得た。この混合溶液にアニオン重合型硬化促進剤（ＴＡＰ）０．５部を高速回転ミキサーで均一に混合し、ワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３０μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱硬化させることにより、樹脂組成物層厚２０μｍの封止用シートを得た。 <Comparative Example 3>
64 parts of polyethylene resin (ACRYFT CM5022, 20% toluene solution) and 35 parts of cyclohexane ring-containing saturated hydrocarbon resin purified product (TFS13-030, 60% toluene solution) are mixed and mixed with a high-speed rotary mixer to obtain a uniform mixed solution. Obtained. To this mixed solution, 0.5 part of an anionic polymerization accelerator (TAP) was uniformly mixed with a high-speed rotary mixer to obtain a varnish. The obtained varnish is uniformly coated with a die coater on the release-treated surface of a PET film (thickness 30 μm) treated with a silicone-based release agent, and is cured by heating at 130 ° C. for 60 minutes. A sealing sheet having a composition layer thickness of 20 μm was obtained.
　実施例および比較例の評価結果を表１に示す。 Table 1 shows the evaluation results of Examples and Comparative Examples.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例の結果から、本発明の封止用樹脂組成物は、接着湿熱耐性および耐透湿性が良好であることが分かる。また加工性も良好で、安定した塗工が可能であった。 From the results of the examples, it can be seen that the encapsulating resin composition of the present invention has good adhesive moist heat resistance and moisture permeability resistance. Also, the processability was good and stable coating was possible.
　本発明の樹脂組成物は、良好な、接着性、接着湿熱耐性を併せ持ち、半導体、太陽電池、高輝度ＬＥＤ、ＬＣＤ、ＥＬ素子等の電子部品の封止に好適に使用され、特に有機ＥＬ素子の封止に好適に使用される。 The resin composition of the present invention has both good adhesiveness and adhesive wet heat resistance, and is suitably used for sealing electronic parts such as semiconductors, solar cells, high-brightness LEDs, LCDs, EL elements, etc., and particularly organic EL elements. It is suitably used for sealing.

Claims (15)

  1. 　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂、（Ｂ）エポキシ樹脂、並びに（Ｃ）粘着付与樹脂を含有することを特徴とする封止用樹脂組成物。 (A) Polyolefin resin modified with (meth) acrylic acid alkyl ester and acid anhydride, (B) epoxy resin, and (C) tackifying resin.
  2. 　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂が、ポリオレフィン系樹脂の主鎖に（メタ）アクリル酸アルキルエステル単位及び酸無水物単位を含むグラフトポリマーが結合したグラフト変性体であり、該グラフトポリマーの数平均分子量が１００以上である、請求項１記載の封止用樹脂組成物。 (A) Polyolefin resin modified with (meth) acrylic acid alkyl ester and acid anhydride, graft polymer containing (meth) acrylic acid alkyl ester unit and acid anhydride unit bonded to the main chain of polyolefin resin The encapsulating resin composition according to claim 1, wherein the encapsulating resin composition is a graft-modified product, and the graft polymer has a number average molecular weight of 100 or more.
  3. 　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂における、（メタ）アクリル酸アルキルエステルのアルキル基の炭素原子数が１～１８である、請求項１または２記載の封止用樹脂組成物。 The number of carbon atoms in the alkyl group of the (meth) acrylic acid alkyl ester in the polyolefin resin modified with (A) (meth) acrylic acid alkyl ester and an acid anhydride is 1-18. Sealing resin composition.
  4. 　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂における酸無水物基の濃度が０．０５～１０ｍｍｏｌ／ｇである、請求項１～３のいずれか１項に記載の封止用樹脂組成物。 The concentration of the acid anhydride group in the polyolefin resin modified with (A) (meth) acrylic acid alkyl ester and acid anhydride is 0.05 to 10 mmol / g, according to any one of claims 1 to 3. The resin composition for sealing as described.
  5. 　（Ｂ）エポキシ樹脂が、エポキシ変性ポリオレフィン系樹脂である、請求項１～４のいずれか1項に記載の封止用樹脂組成物。 (B) The sealing resin composition according to any one of claims 1 to 4, wherein the epoxy resin is an epoxy-modified polyolefin resin.
  6. 　エポキシ変性ポリオレフィン系樹脂におけるエポキシ基濃度が０．０５～１０ｍｍｏｌ／ｇである、請求項５に記載の封止用樹脂組成物。 The sealing resin composition according to claim 5, wherein the epoxy group concentration in the epoxy-modified polyolefin resin is 0.05 to 10 mmol / g.
  7. 　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂および（Ｂ）エポキシ樹脂の合計の含有量が、樹脂組成物中の不揮発分を１００質量％とした場合、５～８０質量％である、請求項１～６のいずれか１項に記載の封止用樹脂組成物。 When the total content of (A) the (meth) acrylic acid alkyl ester and the polyolefin resin modified with an acid anhydride and (B) the epoxy resin is 100% by mass of the nonvolatile content in the resin composition, 5 The encapsulating resin composition according to any one of claims 1 to 6, which is -80 mass%.
  8. 　（Ｃ）粘着付与樹脂の含有量が、樹脂組成物中の不揮発分を１００質量％とした場合、５～８０質量％である、請求項１～７のいずれか１項に記載の封止用樹脂組成物。 The sealing material according to any one of claims 1 to 7, wherein the content of the (C) tackifying resin is 5 to 80% by mass when the nonvolatile content in the resin composition is 100% by mass. Resin composition.
  9. 　（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂の酸無水物基と（Ｂ）エポキシ樹脂のエポキシ基が反応して生じるエステル結合が形成されている、請求項１～８のいずれか１項に記載の封止用樹脂組成物。 The (A) (meth) acrylic acid alkyl ester and an anhydride group of a polyolefin resin modified with an acid anhydride and an ester bond formed by reacting an epoxy group of (B) an epoxy resin are formed. 9. The sealing resin composition according to any one of 1 to 8.
  10. 　有機ＥＬ素子の封止用である、請求項１～９のいずれか１項に記載の封止用樹脂組成物。 The sealing resin composition according to any one of claims 1 to 9, which is used for sealing an organic EL element.
  11. 　支持体上に接着層が形成された封止用シートであって、該接着層が、請求項１～９のいずれか１項に記載の封止用樹脂組成物により形成されている、封止用シート。 A sealing sheet having an adhesive layer formed on a support, wherein the adhesive layer is formed of the sealing resin composition according to any one of claims 1 to 9. Sheet.
  12. 　有機ＥＬ素子の封止用である請求項１１記載の封止用シート。 The sealing sheet according to claim 11, which is used for sealing an organic EL element.
  13. 　有機ＥＬ素子が封止層により封止されている有機ＥＬデバイスであって、該封止層が、請求項１～１０のいずれか１項に記載の封止用樹脂組成物により形成されている、有機ＥＬデバイス。 An organic EL device in which an organic EL element is sealed with a sealing layer, wherein the sealing layer is formed of the sealing resin composition according to any one of claims 1 to 10. Organic EL device.
  14. 　有機ＥＬ素子が封止層により封止されている有機ＥＬデバイスであって、該封止層が、請求項１１または１２に記載の封止用シートの接着層により形成されている、有機ＥＬデバイス。 An organic EL device in which an organic EL element is sealed with a sealing layer, wherein the sealing layer is formed by an adhesive layer of the sealing sheet according to claim 11 or 12. .
  15. 　請求項１～９のいずれか１項に記載の封止用樹脂組成物を含む樹脂ワニスを、支持体上に塗布および加熱乾燥し、（Ａ）（メタ）アクリル酸アルキルエステルおよび酸無水物で変性されたポリオレフィン系樹脂の酸無水物基と（Ｂ）エポキシ樹脂のエポキシ基とが反応によりエステル結合した接着層を形成することを特徴とする、封止用シートの製造方法。 A resin varnish comprising the encapsulating resin composition according to any one of claims 1 to 9 is applied onto a support and heated and dried, and (A) (meth) acrylic acid alkyl ester and acid anhydride are used. A method for producing a sealing sheet, comprising forming an adhesive layer in which an acid anhydride group of a modified polyolefin resin and an epoxy group of (B) an epoxy resin are ester-bonded by a reaction.
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US11674008B2 (en) 2021-04-15 2023-06-13 H.B. Fuller Company Hot melt composition in the form of a film for use in thin film photovoltaic modules

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008222896A (en) * 2007-03-14 2008-09-25 Seiko Pmc Corp Method for producing modified polyolefin resin and aqueous dispersion composition of modified polyolefin resin
JP2011102350A (en) * 2009-11-11 2011-05-26 Kaneka Corp Modified polyolefin resin composition and method for producing the same
JP2011124458A (en) * 2009-12-14 2011-06-23 Kaneka Corp Solar cell-sealing material and solar cell module
JP2011254022A (en) * 2010-06-03 2011-12-15 Kaneka Corp Solar cell sealing material and solar cell module using the same
JP2013221124A (en) * 2012-04-18 2013-10-28 Tosoh Corp Polyarylene sulfide resin composition and composite comprising the same
JP2014237813A (en) * 2013-05-07 2014-12-18 ユニチカ株式会社 Coating agent for cyclic polyolefin material, and laminate body

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4441151B2 (en) * 2000-09-29 2010-03-31 日本製紙株式会社 Modified polyolefin resin, modified polyolefin resin composition and use thereof
JP4473500B2 (en) * 2002-11-15 2010-06-02 日本製紙ケミカル株式会社 Binder resin composition and use thereof
JP2005206779A (en) * 2003-12-26 2005-08-04 Toyo Ink Mfg Co Ltd Aqueous dispersion of composite resin composition for adhesive and adhesive composition
JP2008248055A (en) 2007-03-30 2008-10-16 Kaneka Corp Composition for sealing material, and sealing material
US8653166B2 (en) * 2009-05-19 2014-02-18 Arkema France Encapsulant compositions, methods of manufacture and uses thereof
JP5628499B2 (en) 2009-09-18 2014-11-19 日本水産株式会社 Low salt soy sauce or low salt soy seasoning containing salty taste enhancer
JP5931415B2 (en) 2011-11-24 2016-06-08 三菱重工業株式会社 Pulverized coal burner
CN104039888A (en) * 2012-01-16 2014-09-10 味之素株式会社 Resin composition for sealing
TWI738641B (en) * 2015-03-20 2021-09-11 日商味之素股份有限公司 Manufacturing method of package

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008222896A (en) * 2007-03-14 2008-09-25 Seiko Pmc Corp Method for producing modified polyolefin resin and aqueous dispersion composition of modified polyolefin resin
JP2011102350A (en) * 2009-11-11 2011-05-26 Kaneka Corp Modified polyolefin resin composition and method for producing the same
JP2011124458A (en) * 2009-12-14 2011-06-23 Kaneka Corp Solar cell-sealing material and solar cell module
JP2011254022A (en) * 2010-06-03 2011-12-15 Kaneka Corp Solar cell sealing material and solar cell module using the same
JP2013221124A (en) * 2012-04-18 2013-10-28 Tosoh Corp Polyarylene sulfide resin composition and composite comprising the same
JP2014237813A (en) * 2013-05-07 2014-12-18 ユニチカ株式会社 Coating agent for cyclic polyolefin material, and laminate body

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018162418A (en) * 2017-03-27 2018-10-18 味の素株式会社 Sealing resin composition and sealing sheet
CN110382561A (en) * 2017-03-31 2019-10-25 味之素株式会社 The composition of sealing
KR102578976B1 (en) * 2017-03-31 2023-09-18 아지노모토 가부시키가이샤 Sealing composition
TWI771397B (en) * 2017-03-31 2022-07-21 日商味之素股份有限公司 Composition for encapsulation
KR20190130012A (en) * 2017-03-31 2019-11-20 아지노모토 가부시키가이샤 Sealing Composition
JP7138406B2 (en) 2017-05-31 2022-09-16 リンテック株式会社 Adhesive composition, adhesive sheet, and sealing body
WO2018221572A1 (en) * 2017-05-31 2018-12-06 リンテック株式会社 Adhesive composition, adhesive sheet, and sealed body
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KR20200015451A (en) * 2017-05-31 2020-02-12 린텍 가부시키가이샤 Adhesive Compositions, Adhesive Sheets, and Encapsulations
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JPWO2018221572A1 (en) * 2017-05-31 2020-04-02 リンテック株式会社 Adhesive composition, adhesive sheet, and sealed body
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KR102483012B1 (en) * 2017-05-31 2022-12-29 린텍 가부시키가이샤 Adhesive composition, adhesive sheet, and encapsulant
KR102469843B1 (en) 2017-05-31 2022-11-22 린텍 가부시키가이샤 Adhesive sheet, and encapsulation body
JP7138101B2 (en) 2017-05-31 2022-09-15 リンテック株式会社 Adhesive sheet and sealing body
JPWO2018221510A1 (en) * 2017-05-31 2019-06-27 リンテック株式会社 Sheet adhesive, gas barrier laminate, and sealing body
JP7079839B2 (en) 2018-02-16 2022-06-02 三井化学株式会社 Image display device encapsulant and image display device encapsulation sheet
JPWO2019159830A1 (en) * 2018-02-16 2020-12-17 三井化学株式会社 Image display device encapsulant and image display device encapsulation sheet
WO2019159830A1 (en) * 2018-02-16 2019-08-22 三井化学株式会社 Image display device sealing material and image display device sealing sheet
WO2019181336A1 (en) * 2018-03-22 2019-09-26 東洋紡株式会社 Aqueous dispersion composition
US20220029133A1 (en) * 2018-12-07 2022-01-27 Lg Chem, Ltd Encapsulation composition
CN113412296A (en) * 2019-02-21 2021-09-17 松下知识产权经营株式会社 Composition for optical waveguide cladding, dry film for optical waveguide cladding, and optical waveguide
KR20230104692A (en) 2020-11-13 2023-07-10 아지노모토 가부시키가이샤 sheet for sealing
DE112021005948T5 (en) 2020-11-13 2023-09-21 Ajinomoto Co., Inc. SEALING MESH

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