WO2006080500A1 - Adhesive and luminescent element - Google Patents

Abstract

An adhesive with which an inorganic material, e.g., a glass or metal, and an organic material, e.g., a plastic, are bonded and which has the function of absorbing oxygen through the surfaces to be in contact therewith, and an electronic material such as a luminescent material, obtained using the adhesive. The adhesive has such an oxygen-absorbing function that the oxygen absorption is 0.5 mL/g or more and comprises a cyclized conjugated-diene polymer having a percentage decrease in unsaturated-bond amount of 10% or higher, the percentage decrease indicating the proportion of the number of unsaturated bonds present in the cyclized conjugated-diene polymer to the number of unsaturated bonds in a conjugated-diene polymer in the case where the cyclized conjugated-diene polymer is obtained by cyclizing the conjugated-diene polymer. The luminescent element is characterized by comprising a base, a luminescent-element main body disposed on the base, an encapsulation vessel disposed so as to cover the luminescent element, and an adhesive with which the base is bonded to the encapsulation vessel, the adhesive being that adhesive.

Description

 Adhesive and light emitting device

 Technical field

 The present invention relates to an adhesive and a light-emitting element, and more particularly to an adhesive having an oxygen absorption function and an oxygen absorption function, and a light-emitting element that is hardly affected by oxygen.

 Background art

 [0002] Usually, the functions required of an adhesive are adhesive strength, durability, heat resistance, solvent resistance, and the like. Various adhesives are being developed for the purpose of realizing such functions. As the adhesive, for example, various inorganic materials including solder and welding materials, glue, rubber adhesive, and organic adhesive such as epoxy adhesive are well known. However, there is a demand for an adhesive that has not only the original function of the adhesive as described above but also a special function according to the application. For example, a surgical adhesive having compatibility with a living body is known.

 [0003] On the other hand, a light-emitting element, which is a precise electronic material, deteriorates its characteristics and quality when it comes into contact with oxygen and moisture. For example, this is an organic electoluminescence device (sometimes called an organic EL device). In principle, an organic EL device has a laminated structure in which an organic light emitting layer is disposed between a cathode and an anode. Such an organic EL device has a problem that the organic light emitting layer and electrodes such as an anode contained therein are deteriorated by moisture, oxygen, etc., and the useful life is shortened. For this reason, normally, in order to block the organic light emitting layer in the organic EL element by atmospheric force, the organic light emitting layer is sealed with a container made of a material having excellent oxygen blocking properties, and the inside of the sealed container. In addition, oxygen scavengers such as iron powder are arranged. Many electronic materials other than organic EL devices use metals, which may cause oxidative degradation due to oxygen in the air. For this reason, after storing these electronic materials in a container that blocks oxygen, the inside of the container is evacuated or the inside of the container is replaced with nitrogen or the like.

[0004] Various materials other than iron powder are used as a material for absorbing oxygen and the like entering the sealed container. Oxygen scavengers have been developed. As the developed oxygen absorber, for example, an oxygen-absorbing material composed of polyterpene and a transition metal salt (Patent Document 1), an oxygen-absorbing material composed of polyisoprene and a transition metal salt (Patent Document 2), and ethylene -An oxygen-absorbing material composed of a cyclopentene copolymer and a transition metal salt (Patent Document 3). However, these oxygen scavengers have a problem that the oxygen scavenger itself deteriorates due to oxygen absorption, or the transition metal salt leaks out the oxygen scavenger power.

[0005] Patent Document 1: JP 2001-507045 Gazette International Publication 98,006779 Nonfret

 Patent Document 2: Japanese Patent Laid-Open No. 2003-71992 International Publication 97/032925 Pan Fret

 Patent Document 3: Special Table 2003—504042 International Publication 01/003521 Nonfret

 Disclosure of the invention

 Problems to be solved by the invention

[0006] As described above, various oxygen scavengers have been proposed for light-emitting elements. However, since a sealed container that needs to block oxygen has a portion bonded with an adhesive, Conveniently, the adhesive also has a function of blocking oxygen. The present invention can bond, for example, glass, an inorganic material such as metal, and an organic material such as plastic, which are materials for forming a sealed container in a light emitting element, and also has a function of absorbing oxygen to bond the bonded portion. It is an object of the present invention to provide an adhesive that blocks oxygen permeation, and a light-emitting element that has a long life without deterioration in quality or characteristics.

 Means for solving the problem

[0007] In order to solve the above problems, the present inventors have investigated various polymers, and as a result, the specific conjugated diene polymer cyclized product has an excellent oxygen-absorbing function and various inorganic substances and The inventors have found that it has an excellent adhesion function with organic substances, and have completed the present invention as follows.

[0008] (1) A conjugated-gen polymer cyclized product having an oxygen-absorbing function of oxygen absorption amount of 0.5 mLZg or more and obtained by cyclization reaction of a conjugated-gen polymer, Conjugated polymer comprising a conjugated cyclized polymer having an unsaturated bond reduction rate of 10% or more indicating the number of unsaturated bonds present in the conjugated cyclized polymer with respect to the number of unsaturated bonds in the polymer An adhesive containing a cyclized product.

 (2) The adhesive according to (1), wherein the conjugated cyclized polymer is a modified conjugated cyclized polymer.

 (3) The adhesive according to (2) above, wherein the modified conjugated cyclized polymer has a polar group by modification.

 (4) The adhesive according to (1), wherein the conjugation polymer is a copolymer of a conjugation monomer and another monomer.

 (5) The adhesive according to (1) above, which is the other monomer-powered styrene.

(6) A substrate, a light emitting element body disposed on the substrate, a sealing container disposed so as to cover the light emitting element body, and an adhesive for adhering the substrate and the sealing container A light-emitting element using the adhesive described in (1) above as the adhesive. The invention's effect

 [0009] The adhesive of the present invention has excellent adhesion to organic materials having good adhesion to inorganic materials, particularly to alicyclic structure polymers having good adhesion to general adhesives. Have In addition, the adhesive of the present invention absorbs and removes oxygen that enters from the outside through the bonded portion by being used for bonding containers that have oxygen absorbability and need to realize an oxygen-free state. Can absorb oxygen in the container. Furthermore, the adhesive of the present invention hardly deteriorates even if it absorbs oxygen. Since the light emitting element using the adhesive of the present invention for sealing or adhering is isolated from oxygen in the atmosphere, it can maintain a stable life span for a long period of time.

 Brief Description of Drawings

 FIG. 1 is a schematic cross-sectional explanatory view showing an organic EL element which is an example of a light emitting element of the present invention.

 Explanation of symbols

[0011] 1: Organic EL device

2: Board 3: Light-emitting element body

 4: Sealing container

 5: Adhesive

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0012] The adhesive of the present invention is an adhesive containing a conjugate cyclized polymer. The conjugated gen polymer cyclized product used in the present invention has an oxygen absorption function with an oxygen absorption amount of 0.5 mLZg or more and an unsaturated bond reduction rate of 10% or more, preferably the conjugated gen polymer. The cyclized product is a modified conjugated polymer cyclized product modified with a polar group. The unsaturated bond reduction rate is defined as a conjugated gen polymer with respect to the number of unsaturated bonds in the conjugated gen polymer when a conjugated gen polymer cyclized product is obtained by cyclization reaction of the conjugated gen polymer. The ratio of the number of unsaturated bonds present in the cyclized product is shown.

 [0013] In the present invention, the conjugated conjugated polymer cyclized product plays an important role, and will be described first. The conjugated diene polymer cyclized product used in the present invention can be obtained by cyclization reaction of a conjugated diene polymer in the presence of an acid catalyst, and a ring structure derived from a conjugated diene monomer unit in the molecule. Have. As the conjugation polymer, a homopolymer of a conjugation monomer or a copolymer of different types of conjugation monomers, or a conjugation monomer and another monomer copolymerizable therewith can be used. Mention may be made of copolymers. The conjugation monomer that can be used is not particularly limited. For example, 1,3-butadiene, isoprene, 2,3-dimethyleno-1,3-butadiene, 2-phenol-1,3-butadiene, 1 , 3-pentagen, 2-methinole-1,3-pentagen, 1,3-hexagen, 4,5-jetinole-1,3-octagen, 3-butyl-1,3-octagen and the like. These monomers may be used alone or in combination of two or more. Of these, isoprene is preferred, with 1,3-butadiene and isoprene being preferred.

[0014] Other monomers copolymerizable with the conjugation monomer are not particularly limited. Specific examples include styrene, 0-methyl styrene, p-methyl styrene, m-methyl styrene, 2, 4-dimethyl styrene, ethyl styrene, pt-butynole styrene, α-methino styrene, α-methyl ρ. -Aromatic burrs such as methyl styrene, 0-chloro styrene, m-chloro styrene, p-chloro styrene, p-bromo styrene, 2, 4-dibu-mouthed styrene, and urnaphthalene Monomers; Chain olefin monomers such as ethylene, propylene, and 1-butene; Cyclic olefin monomers such as cyclopentene and 2-norbornene; 1,5-hexagen, 1,6-hexabutadiene , 1,7-octadiene, dicyclopentagen, and 5-ethylidene-2-norbornene and other non-conjugated diene monomers; (meth) acrylic such as methyl (meth) acrylate and ethyl (meth) acrylate Acid ester; (meth) acrylonitrile, (meth) acrylamide and the like. Of these, styrene is preferred, which is an aromatic bulle monomer, and styrene, which is more preferred is α-methylstyrene. These monomers can be used alone or in combination of two or more.

 The content of the conjugation monomer unit in the conjugation polymer is a force appropriately selected within a range not impairing the effects of the present invention. Usually, 40 mol% or more, preferably 60 mol% or more, more preferably 80 mol. % Or more. If the content of conjugation monomer units is too small, it will be difficult to increase the rate of reduction of unsaturated bonds, and oxygen absorption will tend to be poor.

[0015] Specific examples of conjugation polymers include natural rubber (NR), styrene-butadiene rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), isoprene-isobutylene copolymer rubber (IIR). And ethylene-propylene-gen copolymer rubber and butadiene-isoprene copolymer rubber (BIR). Among these, polyisoprene rubber and polyisoprene rubber, which are preferred, are more preferably used.

[0016] The polymerization method of the conjugation polymer may be according to a conventional method. For example, an appropriate catalyst such as a Ziegler polymerization catalyst, an alkyllithium polymerization catalyst, or a radical polymerization catalyst containing titanium or the like as a catalyst component is used. It is used by solution polymerization or emulsion polymerization. The conjugated diene polymer cyclized product used in the present invention can be obtained by subjecting the conjugated diene polymer to a cyclization reaction in the presence of an acid catalyst. As the acid catalyst used in the cyclization reaction, conventionally known acid catalysts can be used, such as inorganic Bronsted acids such as sulfuric acid; fluoromethanesulfonic acid, difluoromethanesulfonic acid, ρ-toluenesulfonic acid, xylenesulfonic acid, and Alkylbenzenesulfonic acid having an alkyl group having 2 to 18 carbon atoms, and organic sulfonic acid compound such as water-free or alkyl ester of the above sulfonic acid; boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride , Aluminum chloride, jetyl aluminum monochloride , Metal halides such as ethyl ether dichloride, aluminum bromide, antimony pentachloride, tandasten hexachloride, and salt iron salt. These acid catalysts may be used alone or in combination of two or more. Among these, P-toluenesulfonic acid and its anhydride, which are preferably organic sulfonic acid compounds, can be used more preferably. The amount of the acid catalyst used is usually from 0.05 to: LO parts by mass, preferably from 0.1 to 5 parts by mass, more preferably from 0.3 to 2 parts by mass, per 100 parts by mass of the conjugate polymer.

[0017] The cyclization reaction of the conjugation polymer is usually performed by dissolving the conjugation polymer in a hydrocarbon solvent and reacting in the presence of an acid catalyst. The hydrocarbon solvent is not particularly limited as long as it does not inhibit the cyclization reaction. Specific examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; and cyclopentane. And alicyclic hydrocarbons such as cyclohexane; and the like. When these hydrocarbon solvents are used for the polymerization reaction of the conjugation monomer, the polymerization solvent can be used as it is as a solvent for the cyclization reaction, and in this case, the polymerization reaction solution after completion of the polymerization reaction is used. A cyclization reaction can be carried out by adding an acid catalyst. The amount of the hydrocarbon solvent used is in a range where the solid content concentration of the conjugated polymer is usually 5 to 60% by mass, preferably 20 to 40% by mass.

 [0018] The cyclization reaction can be performed under pressure, reduced pressure, or atmospheric pressure, but it is desirable to perform the reaction under atmospheric pressure from the viewpoint of ease of operation. If it is performed in an atmosphere of nitrogen or dry argon, side reactions caused by moisture can be suppressed. In the cyclization reaction, the reaction temperature and reaction time may be according to conventional methods. The reaction temperature is usually 50 to 150 ° C, preferably 70 to 110 ° C, and the reaction time is usually 0.5 to 10 hours, preferably 2-7 hours. After carrying out the cyclization reaction, the acid catalyst is deactivated and the acid catalyst residue is removed by a conventional method. Then, if desired, an antioxidant is added to remove the hydrocarbon solvent and unreacted compounds. A solid conjugate cyclized polymer can be obtained.

[0019] The conjugated gen polymer cyclized product used in the present invention is a modified conjugated gen polymer cyclized product (hereinafter abbreviated as a modified conjugated gen polymer cyclized product) as long as the object of the present invention is not impaired. In addition, an unmodified conjugated diene polymer cyclized product may be When it is necessary to distinguish from a cyclized product of a polymer, the unmodified conjugated polymer cyclized product may be referred to as an unmodified conjugated polymer cyclized product. ) Is preferred over the unmodified conjugate cyclized polymer. Among the modified conjugate conjugated polymer cyclized products, preferred are polar group-containing conjugate conjugated polymer cyclized products modified so as to contain polar groups. The polar group is not particularly limited, and examples thereof include an acid anhydride group, a carboxyl group, a hydroxyl group, a thiol group, an ester group, an epoxy group, an amino group, an amide group, a cyan group, a silyl group, and a noble group. Logen etc. are mentioned.

 [0020] Examples of the acid anhydride group or carboxyl group include maleic anhydride, itaconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, acrylic acid, methacrylic acid, and maleic acid. And a group having a structure in which maleic anhydride is attached to cyclized polyisoprene is preferable from the viewpoint of reactivity and economy.

[0021] Examples of the hydroxyl groups include hydroxyalkyl esters of unsaturated acids such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-methylol (meth) Unsaturated acid amides having hydroxyl groups such as acrylamide group, N- (2-hydroxyethyl) (meth) acrylamide group; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and poly Polyethylene glycol monoesters of unsaturated acids such as (ethylene glycol-propylene glycol) mono (meth) talylate; and polyhydric alcohol monoesters of unsaturated acids such as glycerol mono (meth) talylate Group of the structure added to the polymer cyclized product, Of these, hydroxyalkyl esters of unsaturated acids are preferred, and in particular, a group having a structure in which 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate is added to a conjugated cyclized polymer is preferred. . In the present specification, the expression “(meth) atari...” Means a compound or substituent of “atari ...” and / or “metaatari ...”. Examples of vinyl compounds containing other polar groups include, for example, methyl (meth) atrelate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) Examples include attalylate, dimethylaminopropyl (meth) acrylate, (meth) acrylamide, and (meth) acrylonitrile. [0022] The content of the polar group in the conjugated conjugated polymer cyclized product, in particular the polar group-containing conjugated cyclized polymer cyclized product is not particularly limited, but is usually 0. 1 ~ 200 ^ Jimole, girls or 1 ~: Monore, J girls or 5 ~ 50 ^. If this content is too low or too high, the oxygen absorption function tends to be poor. The polar group content can be calculated by assuming that the molar equivalent of the polar group bound to the molecule of the modified conjugate cyclized polymer molecule is 1 mole.

 [0023] The method for producing the modified conjugated gen polymer cyclized product includes (1) a method in which a conjugated gen polymer cyclized product obtained by the above method is subjected to an addition reaction with a polar group-containing vinyl compound, and (2) a polar group. A method obtained by cyclization of a conjugated diene polymer containing benzene by the above-mentioned method, and (3) subjecting a conjugated diene polymer containing a polar group to a conjugated diene polymer containing a polar group to a caro reaction. And (4) a method obtained by subjecting the product obtained by the method (2) or (3) to an addition reaction of a polar group-containing bully compound. Among these, the method (1) is preferable from the viewpoint of easy adjustment of the unsaturated bond reduction rate.

 [0024] The polar group-containing vinyl compound is not particularly limited as long as it is a compound that can introduce a polar group into a conjugated cyclized polymer, for example, an acid anhydride group, a force oxyl group, a hydroxyl group, Preferred are vinyl compounds having a polar group such as a thiol group, an ester group, an epoxy group, an amino group, an amide group, a cyano group, a silyl group, and a halogen.

 Examples of the vinyl compound having an acid anhydride group or a carboxyl group include maleic anhydride, itaconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, attalic acid, methacrylic acid, and maleic acid. Among these, maleic anhydride can be preferably used in terms of reactivity and economy. As the vinyl compound containing a hydroxyl group, for example, hydroxyalkyl esters of unsaturated acids are preferred. Particularly, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred! /, As vinyl compounds. Can be mentioned. As the epoxy group, for example, an aryl group-containing ether such as allyl glycidyl ether is advantageous for introducing an epoxy group by an addition reaction.

[0025] The method of adding a polar group-containing vinyl compound to a conjugated conjugated polymer cyclized product and introducing a polar group derived from the compound is not particularly limited, but the vinyl compound is added. In the case of reacting, a known reaction generally referred to as an addition reaction or a graft polymerization reaction may be followed. This addition reaction is carried out by bringing a conjugated cyclized polymer and a polar group-containing vinyl compound into contact with each other in the presence of a radical generator, if necessary. Examples of the radical generator include peroxides such as di-tert-butyl peroxide, dicumyl peroxide, and benzoyl peroxide; azo-tolyls such as azobisisobutyl-tolyl;

 The addition reaction may be performed in a solid phase or in a solution, but it is preferably performed in a solution from the viewpoint of easy reaction control. Examples of the reaction solvent used include the same inert solvents as those described above for the cyclization reaction. The amount of the polar group-containing vinyl compound varies depending on the reaction conditions, but is appropriately selected so that the content power of the introduced polar group is within the above-mentioned preferred range.

 The reaction for introducing the polar group can be carried out under pressure, reduced pressure or atmospheric pressure, but it is particularly desirable to carry out under atmospheric pressure from the viewpoint of ease of operation. When carried out in an atmosphere of dry nitrogen or dry argon, side reactions derived from moisture can be suppressed. The reaction temperature and reaction time are usually 30 to 250. C, preferably 60-200. C, and the reaction time is usually 0.5 to 5 hours, preferably 1 to 3 hours.

Conjugated polymer cyclized products, except for those that are 100% cyclized, have two types of unsaturated bonds, a linear unsaturated bond present in at least the linear part and a cyclic unsaturated bond in the cyclized part. Has a saturated bond. In the conjugated diene polymer cyclized product, it is considered that the cyclic unsaturated bond part greatly contributes to oxygen absorption, and the linear unsaturated bond part hardly contributes to oxygen absorption. For this reason, a conjugated diene polymer cyclized product having an unsaturated bond reduction rate of the conjugated diene polymer cyclized product of 10% or more is essential as a material for the laminate for a light emitting device of the present invention. The unsaturated bond reduction rate of the conjugated cyclized polymer is preferably 40 to 75%, more preferably 55 to 70%. If the unsaturated bond reduction rate is too low, oxygen absorption tends to deteriorate. The conjugated diene polymer cyclized product has an unsaturated bond reduction rate that is less than or equal to the upper limit of the above preferable range, thereby preventing the conjugated diene polymer cyclized product from becoming brittle and facilitating the production. Suppresses progress, improves transparency, and can be used for many purposes wear. In addition, if the unsaturated bond reduction rate exceeds 50%, adhesiveness is exhibited, and this property can be utilized. In addition, the conjugated conjugated polymer cyclized product may be a mixture of different types of unsaturated bond reduction rates. For example, an unsaturated bond reduction rate of about 10% may be mixed with an unsaturated bond reduction rate of about 60%.

 Here, the unsaturated bond reduction rate is an index that represents the degree to which the unsaturated bond has been reduced by the cyclization reaction at the conjugation monomer unit site in the conjugation polymer, and is determined as follows. It is done. That is, by proton NMR analysis, the ratio of the peak area of the proton directly bonded to the double bond to the peak area of all protons in the conjugation monomer unit portion in the conjugation polymer was measured before and after the cyclization reaction, respectively. And calculate the rate of decrease.

 Now, at the unit site of the conjugation monomer in the conjugation polymer, the total proton peak area before the cyclization reaction is SBT, the peak area of the proton directly bonded to the double bond is SBU, and after the cyclization reaction. When the total proton peak area is SAT and the peak area of the proton peak directly bonded to the double bond is SAU, the peak area ratio (SB) of the proton directly bonded to the double bond before the cyclization reaction is SB = SBUZSBT The peak area ratio (SA) of the proton directly bonded to the double bond after the cyclization reaction is expressed as SA = SAUZSAT. Therefore, the unsaturated bond reduction rate is given by

 (Unsaturated bond reduction rate (%)) = 100 X (SB-SA) / SB

 Is required.

 On the other hand, the degree of cyclization of the conjugated diene polymer can be evaluated by the cyclization rate. The unsaturated bond reduction rate and cyclization rate can be determined by proton NMR measurement according to the methods described in the following documents (i) and (ii).

 (i) M. a. Golub and J. Heller. Can. J. Chem, 41, 937 (1963)

 (ii) Y. Tanaka and H. Sato, J. Poiym. Sci: Poiy. Chem. Ed., 17, 3027 (1979).

[0028] The oxygen absorption amount of the conjugated diene polymer cyclized product used in the present invention is 0.5 mLZg or more, preferably 2 mLZg or more, particularly preferably 5 mLZg or more, and most preferably lOmLZg or more. It is. Oxygen absorption is the amount of oxygen absorbed per lg of conjugated cyclized polymer cyclized when the conjugated conjugated polymer cyclized product is sufficiently absorbed and saturated by oxygen at a temperature of 23 ° C. The amount is expressed in mL. If the amount of oxygen absorbed is small, a large amount of conjugated diene polymer cyclized product is required to stably absorb oxygen for a long period of time. The amount of oxygen absorbed is primarily correlated with the rate of unsaturated bond reduction in the conjugated cyclized polymer.

 [0029] The conjugated diene polymer cyclized product used in the adhesive of the present invention has an oxygen absorption function of oxygen absorption of 0.5 mL / g or more, preferably 2 mLZg or more, more preferably 5 mlZg or more, most preferably 10 mL Zg or more. When the unsaturated bond reduction rate is 10% or more, it is possible to exhibit a highly stable oxygen absorbing function, adhesiveness as an adhesive, durability, and the like.

 [0030] The conjugated conjugated polymer cyclized product preferably has a mass average molecular weight of 5,000 to 500,000, more preferably <is 10,000 to 400,000, and particularly preferably <is 20,000 to 300,000. It is. If the mass average molecular weight is too low, the oxygen absorbability of the conjugated gen polymer cyclized product tends to deteriorate, and if it is too high, it is used when producing the conjugated gen polymer cyclized product or as an adhesive. When used, fluidity and plasticity tend to be small and difficult to handle. The mass average molecular weight is a value in terms of standard polystyrene, measured using gel 'permeation' chromatography.

 [0031] The glass transition temperature (Tg) of the conjugated-gen polymer cyclized product is not particularly limited, and is a force that can be appropriately selected according to the application. Usually, −50 to 200 ° C., preferably −10 to: LOO ° C, more preferably 20 to 90 ° C, particularly preferably 30 to 70 ° C. If the glass transition temperature of the conjugated diene polymer cyclized product is out of the above range, there may be a problem in adhesion and handling properties. When bonding at a high temperature, it is recommended to use an adhesive with a high Tg and a low Tg for use at low temperatures. The Tg of the conjugated-gene polymer cyclized product can be adjusted by appropriately selecting the monomer used as the raw material, the molecular weight of the conjugated-gen polymer cyclized product, and the unsaturated bond reduction rate.

[0032] Although the adhesive of the present invention may be used in any way, it can usually be used as a tacky adhesive. Moreover, it can also be used by mixing with other adhesives. As other adhesives, Natural adhesives such as starch and glue, urea, melamine, phenol, epoxy resin, vinyl acetate resin, polyurethane, polyamide, vinyl chloride resin, talyl resin, and poly It can be mixed with a synthetic resin adhesive such as butyl alcohol or used in a laminated state.

 [0033] In addition to the conjugated-gen polymer cyclized product, the adhesive of the present invention has various additives, for example, an antioxidant and an action for enhancing oxygen absorption, as long as the effects of the present invention are not essentially impaired. Adhesives other than catalysts, photoinitiators, thermal stabilizers, conjugated cyclized polymer adhesives, materials, reinforcing agents, fillers, flame retardants, colorants, plasticizers, UV absorbers, lubricants, desiccants, deodorizers Additives such as an agent, an antistatic agent, an anti-tacking agent, an antifogging agent, and a surface treatment agent can be combined. These additives can be appropriately selected and blended in appropriate amounts from conventionally known additives according to the purpose. The method of blending the additive is not particularly limited, and can be carried out by melting and kneading each component constituting the adhesive or mixing the solution in a solution state and then removing the solvent.

 [0034] In the present invention, those in which the double bond derived from the conjugated diene monomer in the conjugated diene polymer cyclized product remaining without being cyclized tends to be oxidatively deteriorated chemically. Therefore, it is effective to add an anti-oxidation agent to the conjugated polymer cyclized adhesive with a low unsaturated bond reduction rate. The anti-oxidation agent is not particularly limited as long as it is usually used in the field of adhesives, resin materials or rubber materials. Specific examples of the antioxidant include a phenolic acid antioxidant and a phosphite acid antioxidant. Antioxidants may be used alone or in combination of two or more. The content of the antioxidant is preferably 500 ppm or less, more preferably 400 ppm or less, and particularly preferably 300 ppm or less with respect to the conjugated gen polymer cyclized product. When the content of the antioxidant is too large, the oxygen absorbability of the adhesive tends to decrease. The lower limit of the content of the antioxidant is preferably 10 ppm, more preferably 20 ppm. Adhesives containing a conjugated-gene polymer cyclized product that does not contain an antioxidant may deteriorate at high temperatures or may have reduced mechanical strength after absorbing oxygen.

[0035] Typical examples of the catalyst having an action of enhancing oxygen absorption include transition metal salts. Even if the adhesive of the present invention does not contain such a transition metal salt, Although it exhibits sufficient oxygen absorptivity, the oxygen absorptivity is further improved by containing a transition metal salt. However, when used in light-emitting elements, it is necessary to consider that the addition of metal components does not adversely affect the purpose of use. Examples of such transition metal salts include compounds exemplified in Patent Document 1, Patent Document 2, and Patent Document 3. Of these, cobalt oleate (Π), cobalt naphthenate (Π), cobalt 2-ethylhexanoate (Π), cobalt stearate (Π), and cobalt neodecanoate (Π) are preferred 2- Ethyl cobalt hexanoate (Π), cobalt stearate (Π), and cobalt neodecanoate (Π) are preferred. The compounding amount of the transition metal salt is usually 10 to: LO, 000 mass ppm, preferably 20 to 5,000 mass ppm, more preferably 50 to 5,000 mass ppm with respect to the conjugated cyclized polymer. It is.

[0036] The photoinitiator has an action of promoting the start of the oxygen absorption reaction when the oxygen absorber is irradiated with energy rays. Examples of the photoinitiator include those exemplified in Patent Document 3. The amount in the case of blending a photoinitiator is usually 0.001 to 10 mass _^0/0 of the total amount of adhesive of the present invention is preferably 0.01 to 1 mass ^_0/0.

[0037] The adhesive of the present invention can be suitably used as a sealant or an adhesive for a light emitting device. In particular, it is suitable as a sealant or an adhesive for an organic electoluminescence device. Figure 1 shows a light-emitting element, for example, an organic EL element, formed using the adhesive of the present invention. As shown in FIG. 1, the organic EL element 1 includes a substrate 2, a light emitting element body 3, a sealing container 4, and an adhesive 5. The substrate 2 can be formed of, for example, transparent glass. The light emitting element body 3 includes a cathode (not shown), an anode (not shown), and a light emitting layer (not shown) sandwiched between the cathode and the anode, and energizes the cathode and anode. Thus, the light emitting layer is formed so that it can emit light. This light emitting layer can be formed by further having an electron transport layer, a hole transport layer, and a light emitting organic compound-containing layer containing a light emitting organic compound. The sealing container 4 is formed, for example, in a bottomed cylindrical body that covers one end, and can be formed of glass, metal, grease, or the like. The organic EL element 1 shown in FIG. 1 has the container 4 disposed so as to cover the light emitting element body 3 on the substrate 2 having the light emitting element body 3 disposed on the surface, and the lower end of the sealing container 4 Is bonded to the substrate 1 with the adhesive 5 according to the present invention. In this way, the light-emitting element body 3 has the substrate 2, the sealing container 4, the adhesive 5, Sealed in a sealed space. As a result, the adhesive of the present invention has an oxygen absorption function as well as a good adhesion function, and therefore can keep the sealed space in an oxygen-free state. In addition, oxygen present in the sealed space is absorbed by the conjugated cyclized polymer cyclized product in the adhesive, so that the sealed space becomes oxygen-free. Therefore, the light-emitting element sealed in this manner can suppress deterioration with time due to oxygen that is not affected by oxygen, and as a result, a light-emitting element with a long lifetime can be realized.

 [0038] The adhesive of the present invention has excellent adhesiveness not only to ordinary organic materials but also to alicyclic structure-containing polymers. Furthermore, the adhesive of the present invention exhibits excellent adhesion to inorganic materials such as metals and glass by appropriately selecting polar groups. Further, unlike conventional oxygen-absorbing resin materials, the adhesive of the present invention does not require a transition metal or the like for oxygen absorption, and thus has excellent electrical insulation and dielectric properties. As described above, for example, when the adhesive of the present invention is used for adhesion between a sealing container and a substrate in an organic EL element, the adhesive may absorb oxygen that has been transmitted through the adhesive layer in the conventional adhesive. Therefore, oxygen does not enter the sealed container from the adhesive layer. Further, it can absorb oxygen entering through the adhesive force substrate facing the inside of the sealed container, and can always keep the light emitting layer of the organic electoluminescence element in an oxygen-free state. Moreover, if the adhesive of this invention is apply | coated inside a sealing container, or if a light emitting layer is sealed using this, an oxygen absorption effect will improve further.

[0039] The adhesive of the present invention is an adhesive having plasticity, flexibility, elasticity, and tackiness, and is usually applied and adhered to an adhesive surface. Because of its flexibility and elasticity, it is also suitable for bonding flexible materials such as films. By selecting an appropriate group such as a carboxyl group, an acid anhydride group, a hydroxyl group, or an epoxy group as a polar group, a more suitable adhesive can be obtained for metals and glass. The glass surface and the like can be used more suitably if pretreated with a coupling material. Further, even if there are irregularities on the bonding surface, the adhesive plasticity acts and can be used preferably. In particular, when the resin material such as a sealing container is a laminate, the oxygen Noria has a small function. If the adhesive of the present invention is used for the lamination of a resin material, oxygen that has permeated the laminate can be obtained. It can be absorbed on the adhesive surface and exert oxygen barrier function. The adhesive of the present invention is also suitable for use in optical materials because of its high transparency and low deterioration. The

Example

 The present invention will be described more specifically with reference to examples. In the following description, “part” and “%” are based on mass unless otherwise specified.

 Measurement and evaluation of various physical properties and the like were performed as follows.

 (1) Mass average molecular weight

 The weight average molecular weight was determined as a value in terms of standard polystyrene using gel “permeation” chromatography.

 (2) Unsaturated bond reduction rate

 The unsaturated bond reduction rate was determined by the NMR NMR method with reference to the methods described in the following documents (a) and (b).

 (a) M. a. Golub and J. Heller. Can. J. Chem, 41, 937 (1963)

 (b) Y. Tanaka and H. Sato, J. Poiym. Sci: Poiy. Chem. Ed., 17, 3027 (1979)

 At the conjugation monomer unit site in the conjugation polymer, the total peak peak area before the cyclization reaction is SBT, the peak area of the proton directly bonded to the double bond is SBU, and after the cyclization reaction When the total proton peak area is SAT and the peak area of the proton peak directly bonded to the double bond is SAU, the peak area ratio (SB) of the proton directly bonded to the double bond before the cyclization reaction is SB = SBUZSBT The peak area ratio (SA) of the proton directly bonded to the double bond after the cyclization reaction is expressed as SA = SAU / SAT. Therefore, the unsaturated bond reduction rate is calculated as (unsaturated bond reduction rate (%)) = 100 (SB-SA) ZSB.

 (3) Conjugated monomer unit content

 The conjugation monomer unit content (mol%) is determined by ^ H-NMR analysis.

 (4) Polar group content

The polar group content in the conjugated conjugated polymer cyclized product was calculated by a calibration curve method by measuring the characteristic peak intensity of the polar group by Fourier transform infrared absorption spectrum analysis. For example, if the polar group is an acid anhydride group, measure the peak intensity of the acid anhydride group (measured from 1760 to 1780 cm). The content of the acid anhydride group was determined by a calibration curve method. In the case of a carboxyl group, the peak intensity of the carboxyl group (1700 cm was measured and the content of the carboxyl group was determined by a calibration curve method. In the case of an epoxy group, the content of the epoxy group is the same as that of the methylene proton adjacent to the epoxy group. The proton ratio of the methyl group derived from the conjugation monomer was determined by NMR analysis, and the introduction rate (content) was calculated.

(5) Oxygen absorption amount and oxygen absorption rate

 The sample is compression molded at 100 ° C under a nitrogen atmosphere to produce a 120 m thick film. This film is cut into a size of 100 mm × 100 mm to obtain a sample for oxygen absorption. This oxygen-absorbing sample is sealed with 200 mL of air in a three-layer film of polyethylene terephthalate film (PET) Z aluminum foil (Al) Z polyethylene film (PE) with dimensions of 150 mm x 220 mm. Leave it at 23 ° C, measure the oxygen concentration in the bag every 24 hours with an oximeter, and calculate the amount of oxygen absorbed from the amount of oxygen decrease when the oxygen concentration no longer decreases. The oxygen absorption rate is expressed as the amount of oxygen absorbed for 24 hours after the start of measurement. As an oxygen concentration meter, an oxygen analyzer HS-750 manufactured by Neutronics was used. (6) Adhesive strength (peel strength)

 A solution containing the adhesive of each example or the polymer or adhesive of the comparative example on one side of a 188 μm-thick norbornene-based resin film (Zeonor film ZF-14, manufactured by Nippon Zeon Co., Ltd.) A solid content concentration of 30%) was applied so that the thickness after drying was about 20 m, and dried to produce an adhesive substrate A having an adhesive layer. Adhesive layer surface of adhesive substrate A and adhesive substrate B are bonded together and pressed for 2 minutes under the pressure of IMPa under the condition of heating temperature of 80-100 ° C, in accordance with JIS K6854 (1994) The peel adhesion strength was measured using an autography manufactured by Shimadzu Corporation. (In the case of films, the 180 degree peel adhesion test is performed. In other cases, the T type peel adhesion test is performed.)

As the adhesive substrate B, the following was used.

B1: Norbornene-based resin film with a thickness of 2mm

B2: Polypropylene film with a thickness of 2mm

B3: Polyethylene terephthalate film with a thickness of 2mm

B4: White glass with a thickness of 0.7mm (Cowung 1737: manufactured by Dowcoung) B5: Silicon wafer with a thickness of 550 / zm (2.5 inches: manufactured by Shin-Etsu Steel Co., Ltd.) B6: SUS304 plate with a thickness of 2 mm (manufactured by Nippon Steel Corporation)

 When white glass or a silicon wafer was used as the adhesive substrate B, a substrate surface pretreated with a silane coupling agent was used.

(7) Durability of adhesive

 The adhesive of each Example or the polymer or adhesive of Comparative Example is formed into a film having a thickness of 100 to 120 μm. For the molded film, measure the tensile strength of the film before absorbing oxygen and when absorbing 5% by mass of the film's own weight, and calculate the retention rate of the latter with respect to the former. The determination is based on the following criteria. The tensile strength is measured according to JIS K7127 under the conditions of a tensile speed of 50 mmZ. The evaluation criteria were as follows.

○: Retention rate exceeds 70%.

Δ: Retention rate is 50 to 70%.

X: Retention rate is less than 50%.

(Example 1)

Polyisoprene (73% cis-1,4 bond unit, 2% trans-1,4 bond unit 2 2%) cut into 10 mm square in a pressure-resistant reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet pipe 3, 4 bond units 5%, mass average molecular weight 174, 000) 300 kg, together with 卜 Noren 700 kg. After purging the reactor with nitrogen, heat to 85 ° C and completely dissolve the polyisoprene in toluene with stirring. Then, mix the p-toluenesulfonic acid and toluene so that the water content is 150 ppm or less. Then, 2.4 parts of p-toluenesulfonic acid obtained by reflux dehydration was added, and cyclization reaction was performed at 85 ° C. After reacting for 4 hours, 25% aqueous sodium carbonate solution containing 0.83 parts of sodium carbonate was added to stop the reaction. Washing with 300 parts of ion-exchanged water was repeated 3 times at 85 ° C to remove the catalyst residue in the system, and a toluene solution of conjugated polymer cyclized product was obtained. A phenolic antioxidant (Ilganox 1010; manufactured by Chinoku Specialty Chemicals Co., Ltd.) in an amount corresponding to 20 ppm is added to the resulting conjugate solution of conjugated cyclized polymer in the toluene solution. After the addition, a part of toluene in the toluene solution is distilled off, and further vacuum drying is performed to remove toluene. Removal of the conjugated diene polymer cyclized product was separated. The unsaturated bond reduction rate and the mass average molecular weight of this conjugated cyclized polymer were measured. This was used as an adhesive, and the oxygen absorption amount, oxygen absorption rate, adhesive strength, and durability of this adhesive were evaluated. Tables 1 and 2 show the evaluation results.

[0043] (Example 2)

 Except that the amount of p-toluenesulfonic acid used was changed to 2.25 parts and the amount of sodium carbonate added after the cyclization reaction was changed to 0.78 parts, in the same manner as in Example 1, a conjugated gen polymer. A cyclized product was obtained, which was used as the adhesive 2, and the same evaluation as in Example 1 was performed on the adhesive 2. The evaluation results are shown in Tables 1 and 2.

[0044] (Example 3)

 Polyisoprene was changed to high cis polyisoprene with 99% or more of cis 1,4 bond units and a mass average molecular weight of 302,000, and the amount of p-toluenesulfonic acid was changed to 2.16 parts. Except for changing the amount of sodium carbonate to be added later to 0.75 part, a conjugated conjugated polymer cyclized product was obtained in the same manner as in Example 1, and this was used as an adhesive. The same evaluation was performed. The evaluation results are shown in Tables 1 and 2.

[0045] (Example 4)

 Polyisoprene was changed to polyisoprene with a weight average molecular weight of 141,000 consisting of 68% cis-1,4 bond units, 25% trans1,4 bond units and 7% 3,4 bond units. Conjugated polymer cyclization as in Example 1 except that the amount of sulfonic acid used was changed to 2.69 parts and the amount of sodium carbonate added after the cyclization reaction was changed to 1.03 parts. A product was obtained, which was used as an adhesive, and this adhesive was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

[Example 5]

To the conjugated cyclized polymer solution obtained in Example 1, 2.5 parts of maleic anhydride is added to 100 parts of the conjugated cyclized polymer product, and the addition reaction is performed at 160 ° C. for 4 hours. I did it. After a part of toluene in the solution was distilled off, an amount of phenolic antioxidant equivalent to 20 ppm (Ilganox 1010; manufactured by Tino 'Specialty Chemicals) was added to the conjugated cyclized polymer, Further, vacuum drying is performed to remove toluene and unreacted Hydromaleic acid was removed to obtain a modified conjugate conjugated polymer cyclized product. Unsaturated bond reduction rate, weight average molecular weight, and polar group content of the resulting modified conjugate cyclized product were measured. The modified conjugate cyclized polymer was used as an adhesive, and this adhesive was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

[Example 6]

 Polyisoprene was changed to high cis polyisoprene with 99% or more of cis 1,4 bond units and a mass average molecular weight of 302,000, and the amount of p-toluenesulfonic acid was changed to 2.16 parts. A modified conjugate conjugated polymer cyclized product was obtained in the same manner as in Example 5 except that the amount of sodium carbonate to be added later was changed to 0.75 part. Unsaturated bond reduction rate, mass average molecular weight, and polar group content of this modified conjugate cyclized product were measured. This modified conjugate cyclized polymer was used as an adhesive, and the adhesive was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

[0048] (Example 7)

 Polyisoprene was changed to polyisoprene with a weight average molecular weight of 141,000 consisting of 68% cis-1,4 bond units, 25% trans1,4 bond units and 7% 3,4 bond units. The modified conjugate conjugated polymer ring was changed in the same manner as in Example 5 except that the amount of sulfonic acid used was changed to 2.69 parts and the amount of sodium carbonate added after the cyclization reaction was changed to 1.03 parts. The compound was obtained. Unsaturated bond reduction rate, weight average molecular weight, and polar group content of this modified conjugate cyclized product were measured. Using this modified conjugated cyclized polymer as an adhesive, this adhesive was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

[0049] (Example 8)

In an autoclave equipped with a stirrer, 8000 g of cyclohexane, 320 g of styrene, and 19.9 mmol of hexane solution of 1.5-mol Z liter concentration were added, and the internal temperature was raised to 60 ° C for 30 minutes. Polymerized. The polymerization conversion rate of styrene was almost 100%. A part of the polymerization solution was sampled and the mass average molecular weight of the obtained polystyrene was measured and found to be 14,800. Subsequently, 1840 g of isoprene was continuously added over 60 minutes while controlling the internal temperature so as not to exceed 75 ° C. After addition is complete, continue at 70 ° C for an additional hour I adapted it. The polymerization conversion rate at this point was almost 100%. To the above polymerization solution, add 0.32 g of 1% aqueous solution of sodium salt of j8 naphthalenesulfonic acid-formalin condensate to stop the polymerization reaction, and a block of diblock structure consisting of polystyrene block and polyisoprene block. Copolymer _a was obtained. A part of this was sampled and the weight average molecular weight was measured, and it was 178,000. Subsequently, 18.4 g of xylene sulfonic acid was added to the polymer solution containing the block copolymer a, and a cyclization reaction was performed at 80 ° C. for 4 hours. Thereafter, a 25% aqueous solution of sodium carbonate containing 6.2 g of sodium carbonate was added to stop the cyclization reaction, and the mixture was stirred at 80 ° C. for 30 minutes to obtain a crude solution containing a conjugated diene polymer cyclized product. The resulting crude solution was filtered using a glass fiber filter with a pore size of m to remove the cyclization catalyst residue, and a solution containing a conjugated conjugated polymer cyclized product, which was cyclized product A of the block copolymer, was obtained. Obtained. To 1000 parts of this solution, Irganox 1010 (manufactured by Ciba 'Specialty' Chemicals) 0.06 part was added as an anti-aging agent, and then the solvent was distilled off while stirring at 120 ° C to obtain a solid. When the partial concentration reached 85% by mass, the temperature was raised to 160 ° C., and the solvent was completely removed under reduced pressure to separate the conjugated conjugated polymer cyclized product. Unsaturated bond reduction rate, conjugation monomer (here, isoprene) unit content and mass average molecular weight of this conjugated conjugated polymer cyclized product were measured. The conjugated-gen polymer cyclized product was used as an adhesive, and this adhesive was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

(Example 9)

While stirring 1000 parts of the solution containing the conjugated cyclized polymer obtained in Example 8, the solvent was distilled off at 120 ° C. until the solid content concentration reached 80% by weight to obtain a concentrated solution. . Next, 4.41 parts of maleic anhydride was added to this concentrated solution, and an addition reaction was performed at 160 ° C. for 1 hour. Thereafter, unreacted maleic anhydride and solvent were removed at 160 ° C, and phenol antioxidant (Irganox 1010; manufactured by Tinoku Specialty Chemicals Co., Ltd.) was added by 0.062 part. The obtained liquid material was transferred to a container having a tetrafluorinated styrene resin coating. The contents of the container were dried under reduced pressure at 75 ° C. to obtain a conjugated conjugated conjugated polymer cyclized with maleic anhydride. Unsaturated bond reduction rate of the resulting modified conjugate cyclized polymer, conjugation monomer (here isoprene) unit content, polarity The group content and the mass average molecular weight were measured. The modified conjugate cyclized polymer was used as an adhesive, and this adhesive was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

[Example 10]

 The toluene solution of the conjugated cyclized polymer synthesized in Example 1 was heated to 130 ° C. in a nitrogen atmosphere to distill off about 80% of toluene. 15 parts of allyl glycidyl ether was added to the solution after distillation to make it uniform. Further, the temperature inside the reactor was raised to 160 ° C, and toluene was distilled off. After toluene distillation was completed, the reaction was further continued for 1 hour to carry out the addition reaction of the aryl group, and the epoxy group was introduced. After the temperature of the conjugated diene polymer cyclized product was cooled to around 80 ° C, the conjugated diene polymer cyclized product was redissolved in toluene so that the concentration of the conjugated diene polymer cyclized product was 8%. . The conjugated cyclized polymer solution was dropped into an isopropyl alcohol solution containing Ilganox 1010 at a ratio of lOOOppm to solidify the conjugated cyclized polymer cyclized product to remove unreacted allylic glycidyl ether. By drying under reduced pressure at 75 ° C., a modified conjugate conjugated polymer cyclized product modified with an epoxy group was obtained. Unsaturated bond reduction rate, conjugation monomer (here isoprene) unit content, mass average molecular weight, and polar group content of this modified conjugate cyclized product were measured. Using this modified conjugated cyclized polymer as an adhesive, this adhesive was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2. In addition, all of the conjugated-gene polymer cyclized products obtained in Examples 8 to 10 described above did not substantially contain a gel insoluble in toluene.

 [0052] (Comparative Example 1)

Prepare a 30% toluene solution of polyisoprene (73% cis 1,4 bond unit, 22% trans 1,4 bond unit, 5% 3,4 bond unit, mass average molecular weight 174,000) under nitrogen atmosphere. Then, it was applied on a polyethylene terephthalate film having a thickness of 50 μm and dried to form a polyisoprene film having a thickness of 120 μm, thereby obtaining a laminated film. The formed polyisoprene film was peeled off from the obtained laminated film and cut into 100 mm XI 00 mm to obtain test pieces. Using the test piece, the oxygen absorption amount and the oxygen absorption rate were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2. This comparative example Is related to the case where the cyclization reaction is not performed and the unsaturated bond reduction rate is 0%.

[0053] (Comparative Example 2)

 A 20% toluene solution of β-vinene polymer (YS resin ΡΧΝ-1150Ν; manufactured by Yasuhara Chemical Co., Ltd.) was prepared, and then purified by precipitation with methanol to obtain a -vinene polymer from which the antioxidant was removed. A laminated film and a test piece were obtained and evaluated in the same manner as in Comparative Example 1 except that | 8-vinene polymer from which the antioxidant was removed was used instead of polyisoprene. The evaluation results are shown in Tables 1 and 2. This comparative example relates to the case of using a polymer that is not a conjugated conjugated polymer cyclized product.

[Comparative Example 3]

In accordance with Example 16 of Patent Document 3, to obtain ethylene-cyclopentene copolymer cyclopentene units is 15.5 mole _^0/0 (weight average molecular weight = 83, 500). Under a nitrogen atmosphere, a 30% toluene solution of the ethylene-cyclopentene copolymer was prepared, applied onto a polyethylene terephthalate film having a thickness of 0 μm, dried, and then the ethylene-cyclopentene copolymer having a thickness of 120 μm was dried. A polymer film was formed to obtain a laminated film. The formed ethylene-cyclopentene copolymer film was peeled off from the obtained laminated film and cut into 100 mm × 100 mm to obtain test pieces. Evaluation was performed in the same manner as in Comparative Example 1 except that the test piece was used instead of the polyisoprene film. The evaluation results are shown in Tables 1 and 2. This comparative example relates to the case where a polymer that is not a conjugated cyclized polymer is used.

[0055] (Comparative Example 4)

Prepare a 30% toluene solution of polyisoprene (73% cis 1,4 bond unit, 22% trans 1,4 bond unit, 5% 3,4 bond unit, mass average molecular weight 174,000) under nitrogen atmosphere. In addition, cobalt neodecanoate was added to the polyisoprene so that the cobalt metal content was 1, OOOppm. This solution was applied onto a polyethylene terephthalate film having a thickness of 50 μm and then dried to form a polyisoprene film having a thickness of 120 μm to obtain a laminated film. The formed polyisoprene film was peeled from the obtained laminated film and cut into 100 mm × 100 mm to obtain test pieces. The test piece was evaluated in the same manner as in Comparative Example 1. The evaluation results are shown in Table 1 and Table 2. . This comparative example relates to the case where the cyclization reaction was not performed and the unsaturated bond reduction rate was 0%.

 [0056] (Comparative Example 5)

 After preparing a 20% toluene solution of β-vinene polymer (YS resin ΡΧΝ-1150Ν; manufactured by Yasuhara Chemical Co., Ltd.), precipitation purification with methanol was performed to obtain a pinene polymer from which the antioxidant was removed. In a nitrogen atmosphere, prepare a 30% toluene solution of j8-pinene polymer from which the antioxidant has been removed. I was jealous. This solution was applied onto a polyethylene terephthalate film having a thickness of 50 μm, and then dried to form a film having a thickness of 120 μηι (Ό β-vinene polymer, thereby obtaining a laminated film. The formed polymer film was peeled from the laminated film and cut into 100 mm × 100 mm to obtain test pieces, which were evaluated in the same manner as in Comparative Example 1. Evaluation The results are shown in Tables 1 and 2. This comparative example relates to the case where a polymer that is not a conjugated conjugated polymer cyclized product is used.

[0057] (Comparative Example 6)

In accordance with Example 16 of Patent Document 3, to obtain ethylene-cyclopentene copolymer cyclopentene units is 15.5 mole _^0/0 (weight average molecular weight = 83, 500). In a nitrogen atmosphere, a 30% toluene solution of the ethylene-cyclopentene copolymer was prepared, and cobalt neodecanoate was added to the ethylene-cyclopentene copolymer so that the cobalt metal was 1, OOOppm. I was jealous. The solution was applied onto a polyethylene terephthalate film having a thickness of 50 m and then dried to form a film of an ethylene-cyclopentene copolymer having a thickness of 120 m to obtain a laminated film. The formed co-ethylene-cyclopentene polymer film was peeled from the obtained laminated film, and cut into lOOmm × 100 mm to obtain a test piece. Evaluation was performed in the same manner as in Comparative Example 1 using the test piece. The evaluation results are shown in Tables 1 and 2. This comparative example relates to the case of using a polymer that is not a conjugated cyclized polymer.

[0058] (Comparative Example 7)

Stir 1000 parts of the solution of block copolymer a obtained in Example 8 (solid content concentration = 29.9%) However, the solvent was distilled off at 120 ° C. until the solid concentration reached 80% by mass. To this, 4.41 parts of maleic anhydride was added, and an addition reaction was performed at 160 ° C. for 1 hour. Thereafter, unreacted maleic anhydride and solvent were removed at 160 ° C, and phenolic acid / anti-oxidation agent (Irganox 1010; manufactured by Chinoku 'Specialty' Chemicals) was added after 0.062 parts. Then, it was transferred to a container with a tetrafluorinated styrene resin coating. It was dried under reduced pressure at 75 ° C. to obtain a modified styrene isoprene block copolymer to which anhydrous maleic acid was attached. The mass average molecular weight and polar group content of the variable copolymer were measured. Using this modified styrene isoprene block copolymer as an adhesive, the same evaluation as in Example 1 was performed. The evaluation results are shown in Tables 1 and 2. This comparative example relates to the case where the cyclization reaction is not performed and the unsaturated bond reduction rate is 0%.

[0059] [Table 1]

 *: Value when cobalt salt is added to the resin

[0060] [Table 2] Peel strength (g Z lOmm width) Adhesion temperature

 durability

B1 B2 B3 B4 B5 B6 [° C] Example 1 1000 <1000 <650 XX 450 100 〇 Example 2 1000 <1000 650 XX 100 〇 Example 3 1000 <1000 <550 XX 450 100 〇 Example 4 1000 < 1000 <500 XX 400 100 ○ Example 5 1000 <1000 <650 950 700 1000> 80 Example 6 1000 <1000 <650 900 620 900 80 ○ Example 7 1000 <1000 <550 850 670 900 80 ○ Example 8 1000 <1000 <550 XX 500 100 ○ Example 9 1000 <1000 <560 780 500 850 100 ○ Example 10 1000 <1000 <650 900 650 900 100 ○ Comparative example 1 300 350 400 XX 300 100 X Comparative example 2 350 300 XXXX 100 X Comparative Example 3 300 500 300 XX 300 100 X Comparative Example 4 300 330 350 XXX 100 X Comparative Example 5 300 300 XXXX 100 X Comparative Example 6 300 300 350 XXX 100 X Comparative Example 7 200 400 X 400 300 350 100 Δ Note) In the table, the peel strength X means that there is no adhesive strength (peel strength 200 g or less).

[0061] As shown in the above results, the adhesive using the conjugated diene polymer cyclized product of the present invention has a sufficient adhesion function and durability, and has an oxygen absorption function and includes an adhesion surface. The sealed space can be brought into a state close to anoxic state.

 Industrial applicability

[0062] The adhesive of the present invention can be used as an adhesive for light-emitting elements and the like, and can be particularly suitably used as an adhesive for containers for creating an oxygen-free state.

Claims

The scope of the claims  [1] A conjugated diene polymer cyclized product having an oxygen absorption function of oxygen absorption amount of 0.5 mLZg or more and obtained by cyclization reaction of a conjugated diene polymer, An adhesive comprising: a conjugated diene polymer cyclized product having an unsaturated bond reduction rate of 10% or more indicating the number of unsaturated bonds present in the conjugated diene polymer cyclized product relative to the number of saturated bonds.  [2] The adhesive according to claim 1, wherein the conjugated cyclized polymer is a modified conjugated cyclized polymer.  [3] The adhesive according to [2], wherein the modified conjugate conjugated polymer cyclized product has a polar group by modification.  [4] The adhesive according to claim 1, wherein the conjugation polymer is a copolymer of a conjugation monomer and another monomer. 5. The adhesive according to claim 1, wherein the other monomer is styrene. [6] a substrate, a light emitting element body disposed on the substrate, a sealing container disposed so as to cover the light emitting element body, and an adhesive bonding the substrate and the sealing container A light emitting device comprising the adhesive according to claim 1 as the adhesive.