TW201016813A - Adhesive composition - Google Patents

Abstract

An adhesive composition that simultaneously satisfies high transparency and high adhesive strength is provided. The adhesive composition includes an epoxy resin having no carbon-carbon unsaturated bond, an acid anhydride, a carbonate compound having no carbon-carbon unsaturated bond and having a group capable of reacting with an epoxy group or an acid anhydride, and a curing accelerator. The adhesive composition contains 5 to 100 parts by weight of the carbonate compound based on 100 parts by weight of the epoxy resin.

Description

201016813 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an adhesive composition, and more particularly to an adhesive composition capable of providing a transparent cured product. [Prior Art] Adhesives for monthly transparent curing products are heretofore required in the field of optical devices. For example, 'transparency is necessary for bonding adhesives of individual parts of an optical display device (such as a liquid crystal display device and a plasma display device), or transparency is used in a light-emitting device using a light-emitting diode (LED) for bonding LED elements and The adhesive for the substrate is required. As an adhesive composition for providing a transparent cured product, a composition containing an epoxy compound, a monoanhydride, and an organophosphorus or sulfur-based curing accelerator is known. When adhesion is considered, an amine, imidazole or diazabicyclo-ene (DUB) or a salt thereof is used as a curing accelerator. Adhesive compositions comprising a metal carboxylate salt are also well known. The unexamined patent publication No. 56-167724 describes a method for producing an epoxy resin using a half vinegar obtained from an acid anhydride, a polyol compound and zinc sulphate. Japanese Unexamined Patent Publication No. 11274571 describes the high adhesion strength obtained by a method using an acid anhydride, a polyol compound, a slow acid word, and a compound compound. SUMMARY OF THE INVENTION An adhesive composition which simultaneously satisfies the requirements of high transparency and high adhesion strength is extremely necessary in the field of optical devices. The present invention 143089.doc 201016813 provides such an adhesive composition. The invention includes the following aspects. (1) An adhesive composition comprising an epoxy resin having no carbon-carbon unsaturated bond, an acid anhydride, a group having no carbon-carbon unsaturated bond and having a reactive group with an epoxy group or an acid anhydride A carbonate compound, and a curing accelerator, wherein the adhesive composition comprises 5 to 100 parts by weight of a carbonate compound based on 100 parts by weight of the epoxy resin. (2) The adhesive composition according to (1), wherein the carbonate compound is represented by the following formula (A): [Chemical Formula 1]

Wherein R1 represents a divalent hydrocarbon-containing group or a covalent bond; R2 each independently represents a divalent hydrocarbon-containing group; R3 represents a monovalent hydrocarbon-containing group or R4_X, wherein when R3 is a monovalent hydrocarbon-containing group, 'R3 does not contain X, R4 Represents a divalent hydrocarbon-containing group or a covalent bond 'and R1 'R2, R3 and R4 have no carbon-breaking unsaturated bond; X represents a group reactive with an epoxy group or an acid anhydride; and η represents 1 or more The integer. (3) The adhesive composition of (2), wherein R3 is r4_x. (4) The adhesive composition according to any one of (1) to (3) wherein X is a carboxyl group, a hydroxyl group, an amine group, or a fluorenyl group. (5) The adhesive composition as in (4) wherein R1, R2 & R4 are an aliphatic group. (6) The adhesive composition according to (5), wherein R1, R2 and R4 further comprise 143089.doc 201016813 ester group, carbonate group or decylamino group. (7) The adhesive composition according to any one of (1) to (6) wherein the ring is an alicyclic epoxy compound or a hydrogenated cyclic hydrazine compound. The adhesive composition of any one of (1) to (7) wherein the acid liver is non-aromatic and does not contain a carbon-carbon unsaturated bond. (9) The adhesive composition according to any one of (1) to (8) wherein the acid liver is a polycarboxylic acid anhydride. (10) The adhesive composition according to any one of (1) to (9), which comprises 50 to 15 parts by weight of an acid anhydride and 1 to 2 parts by weight of a curing accelerator based on 1 part by weight of the epoxy resin. Agent. (11) The adhesive composition according to any one of (1) to (10) which further comprises an antioxidant. (12) A light-emitting device comprising a substrate, a light-reflecting layer on the substrate, an adhesive layer made of the adhesive composition according to any one of (1) to (11), and a light-emitting layer The element, the light reflecting layer on the substrate is bonded to the light emitting element by an adhesive layer. (13) The light-emitting device of (12), wherein the light-emitting element is an lEd wafer and the light-emitting device is a light-emitting diode. (14) An optical display device comprising a member joined using the adhesive composition according to any one of (1) to (11). [Embodiment] In the present disclosure, a cured product having a polymer structure having a carbonate structure can be obtained by using a carbonate compound containing a functional group reactive with an epoxy compound and/or an acid anhydride, and thus improving the adhesion strength. No 143089.doc 201016813 Damage and transparency. One aspect of the present disclosure is an adhesive composition comprising an epoxy resin having no carbon-carbon unsaturated bond, an anhydride, a carbon-carbon unsaturated bond, and an epoxy group or An acid anhydride-reactive group of a carbonated compound, and a curing accelerator, wherein the composition comprises 5 to 100 parts by weight of a carbonate compound based on 1 part by weight of the epoxy resin. In the present application, the term "having no carbon-carbon unsaturated bond" means that the structure of the main component does not include "C=c" or "c=c". It is more rigorously defined to use a value such as a broken value in a method of defining a carbon-carbon unsaturated bond content. According to this method, the amount of the carbon-carbon unsaturated bond reacted with the reagent is measured using Wijs or Hanus reagent. In the present application, if a compound containing no carbon-carbon unsaturated bond is obtained by a several-stage synthetic synthesis method, and the starting material or the intermediate of the compound has a structure capable of reacting with the Wijs or Hanus reagent, then there is no carbon. The compound of the carbon unsaturated bond means that the compound has a ruthenium or greater and an iodine value of 2 or less (the value determined by the Wijs method defined in ASTM 1959-97). When the starting material or intermediate has a carbon-carbon unsaturated bond, but for some reason (eg, high resonance stabilization, steric hindrance) (when the structure does not contain carbon-carbon unsaturated bonds by having a resonant structure ( For example, when the carbon-carbon unsaturated bond of the benzene ring is hydrogenated and hydrogenated, no hydrogenation occurs, and the structure of the carbon-carbon unsaturated bond remains in the resin when it is not reacted with the reagent for measuring the value (impurity) The amount means a value of 1,000 ppm or less (measured by a gas chromatography mass spectrometer). The ring having no carbon-carbon unsaturated bond used in the present disclosure 143089.doc 201016813 The oxygen resin is used as a matrix resin in the adhesive composition. "Carbon-carbon unsaturated bond" means "c=c" or "c=c". In the present disclosure, the carbon-carbon unsaturated bond is not present in any linear or cyclic portion of the epoxy resin. And in the substituents. An epoxy resin having no glycidyl ether group can be commercially available as an epoxy resin having no carbon-carbon unsaturated bond (wherein a carbon-carbon unsaturated bond is obtained by using a bisphenol glycidyl ether main component which is widely used) The benzene ring of the chain is hydrogenated and removed.] For example, hydrogenated bisphenol glycidyl ether (manufactured by Adeka Corporation under the trade name "EP-4080S" is manufactured by japan Ep0Xy Resin K.K. under the trade name "YX-8000". ), hydrazine, 4_cyclohexane dimethanol diglycidyl ether (manufactured by New Japan Chemical Co. Ltd. under the trade name "DME-100"), dicyclopentadiene dimethanol diglycidyl ether (by Adeka) Corpion is manufactured under the trade name "EP-4088S", hexahydrophthalic acid diglycidyl ether (manufactured by Nippon Kayaku Co., Ltd. under the trade name "AK-601"), and two (2) , 3-epoxypropyl) isocyanuric acid (manufactured by Nissan Chemical Industries, Ltd. under the trade name "TEPIC"). As the alicyclic epoxy resin, for example, 3,4-epoxycyclohexylmethyl-3,4-oxocyclohexyl acid vinegar (manufactured by Daicel Chemical Industries, Ltd. under the trade name of CEL2021P), 2,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-(2-cycloindoleyl)cyclohexane calcined product (from Daicel Chemical Industries, Ltd.) EHPE-3 150" is manufactured by the trade name), and 1,2:8,9-epoxy citrate (produced by Daicel Chemical Industries, Ltd. under the trade name "CEL3000"). The viscosity and glass transition temperature after curing are 143089.doc 201016813, 3,4-epoxycyclohexylfluorenyl_3,4,-epoxycyclohexyl phthalic acid vinegar is preferred because of the use of high glass When converting the temperature of the epoxy resin, it is easy to ensure the adhesion strength at high temperatures. The epoxy resin can be used alone, or when considering the glass transition temperature and viscosity, two or more of these rings can be used. A combination of resins. As an epoxy resin adhesive, a resin containing an aromatic epoxy resin as a main component has been hitherto used, for example, a double A-type epoxy resin (DGEBA) or double-type F-type epoxy resin (DGEBF). However, since these resin primary bonds contain a benzene ring, the double bond of the benzene ring breaks with time, and thus resin discoloration occurs. When the resin composition of the aromatic epoxy resin is used, the transparency thereof is greatly reduced due to discoloration (yellowing) with time. Since the epoxy resin used in the present invention does not contain a double bond, the above does not occur. The adhesive composition includes an acid anhydride. The acid anhydride is used to cure an epoxy group of an epoxy resin. The curing agent is preferably an acid anhydride having no carbon-carbon unsaturated bond. Examples of the acid anhydride include hexahydrophthalic acid. Anhydride (manufactured by New Japan Chemical Co., Ltd. under the trade name "RIKACID HH"), 4·methyl hexahydrophthalic anhydride or an acid anhydride containing the same group (by New

Japan Chemical Co., Ltd. is manufactured under the trade name "MH700", manufactured by Hitachi Chemical Co" Ltd. under the trade name "HN-5500", and weathered methyl nadic anhydride (by New Japan Chemical Co., Ltd. is manufactured under the trade name "RIKACID HNA-100". The acid anhydride may be used singly as a curing agent' or may be used in combination of two or more curing agents. In view of the glass transition temperature (storage stability) of the adhesive composition, the acid 143089.doc 201016813 is preferably used in an amount of from 5 Å to 15 parts by weight based on 100 parts by weight of the epoxy resin. The adhesive composition includes a carbonic acid compound carbon-carbon which does not have a carbon-carbon unsaturated bond and which is also reactive with an epoxy resin or an acid anhydride. The carbonate compound is usually represented by the following general formula (A): [Chemical Formula 2]

Wherein R1 represents a divalent hydrocarbon-containing group or a covalent bond; R2 each independently represents a divalent hydrocarbon-containing group; R3 represents a monovalent hydrocarbon-containing group or R, x, and R4 represents a divalent hydrocarbon-containing group or a covalent bond, provided that R1, R2, R3 and R4 have no carbon-carbon unsaturated bond; X represents a group reactive with an epoxy group or an acid anhydride; and η represents an integer of 1 or more. X, that is, a group reactive with an epoxy group or an acid group is, for example, a group reactive with an epoxy group. When X reacts with an epoxy group, the carbonate compound becomes compatible with the epoxy resin, and thus transparency can be ensured. X may be, for example, a carboxyl group, a hydroxyl group, an amine group, a decyl group, a decyl group, or a tooth atom and is preferably a buffer group, a trans group, an amine group or a carbyl group because these functional groups are at a temperature of about 100 ° C with a ring. The oxy group reacts irreversibly and rapidly. More preferably, it is a carboxyl group or a hydroxyl group, since it does not contain nitrogen and does not contain a group which is less likely to cause discoloration, even after long-term heat resistance test. R1, R2 and R4 are divalent hydrocarbon-containing groups or covalent bonds. R1 is a divalent organic group to bond the oxygen atom of the polycarbonate to X, or a covalent bond. The above-mentioned divalent has a 1430S9.doc 201016813 machine group which does not contain a *saturation bond in the structure. Rl is a hydrocarbon-containing group and may include rabbits and hydrogen hydrides and other heteroatoms such as oxygen nitrogen, dish, and Shi Xi. When a hetero atom is included, an ester, carbonate, decylamine or urea group can be formed. R1 preferably includes a rigid structure of smoke, such as a cyclohexene backbone, a norbornene backbone. R is an organic map to join the oxygen atoms in the polycarbonate with R3. The divalent organic based ffl structural towel does not contain a lanthan and a bond. The r2 is a hydrocarbon-containing group and may include a hetero atom other than carbon and hydrogen, such as oxygen, nitrogen, lin, and lanthanum. When /, including heteroatoms, vinegar, carbonated acid, amine or knee base can be formed. Preferably, it comprises a rigid hydrocarbon of a cyclic hydrocarbon, also 丨α 1 ^ , , such as a cyclohexane main chain or a norbornene main R3 system R4-X or a monovalent organic group. The monovalent organic group structure does not include an unsaturated bond. R3 is a hydrocarbon-containing group and may include heteroatoms other than carbon and hydrogen, such as oxygen 'nitrogen, phosphorus, and riding. When a hetero atom is included, vinegar, carbonated acid, guanamine or glandular group can be formed. R3 preferably includes a rigid structure of the ring smoke, such as a cyclohexene backbone or a hardened and norbornene backbone. R4 bonds the divalent organic group of R2 to hydrazine. Residues and bonds are not included in the divalent organic radical structure. The R4-containing hydrocarbon group U may include heteroatoms other than carbon and hydrogen, such as oxygen, nitrogen, dish, and Shixia. When it includes a hetero atom, it may form a structure including a cyclic hydrocarbon such as a cyclohexane main chain or a norbornene main chain. A compound having a group capable of reacting with an epoxy group at both ends and having a group in which the R3 is more preferably a group or an acid anhydride is preferably represented by the following formula. [Chemical Formula 3] 143089.doc •10- 201016813 X/

R4-X more preferably 'X is a carboxyl group or a hydroxyl group. In particular, the following chemical formulas are listed as examples. [Chemical Formula 4]

R is hydrogen or methyl

Further, the carbonate compound is preferably a solid at room temperature because it is considered that when the carbonate compound is a solid, the decrease in the Tg value can be suppressed, even when the amount thereof is increased. The amount of the carbonate compound added is 5 to 重量 parts by weight based on 100 parts by weight of the epoxy resin. The adhesive strength of the adhesive composition is improved by adding the amount of the carbonate compound after the curing to the above range. 143089.doc 201016813 In the present disclosure, the adhesive composition further includes a curing accelerator. The curing accelerator can effectively suppress the curing temperature. As the curing accelerator, for example, an amine-based curing accelerator, an imidazole-based curing accelerator, a phosphine-based curing accelerator, a ruthenium-based curing accelerator, and a ruthenium-based curing can be used. Promoter and curing accelerator based on bismuth. The phosphine-based curing accelerator and the scaly curing accelerator are more preferable in view of transparency and viscosity of the cured product. As the curing accelerator, an organometallic-based curing accelerator can be used. As the core to the metal, it is preferable to use aluminum, zinc, and the like. When the oxygen-burning group as a ligand is used for an epoxy resin or an acid anhydride, it is not possible to give a waiting time because the reactivity is too high. Therefore, the curing accelerator is preferably a curing accelerator coordinated with acetamidine acetone, or the curing accelerator is in the form of a carboxylate such as a metal soap. These curing accelerators may be used singly or in combination of two or more curing accelerators. The curing accelerator is preferably used in an amount of 0.05 to 20 parts by weight based on 1 part by weight of the epoxy resin, in view of curing heat resistance, weather resistance, and curable property (for example, 15 〇c) of the resin composition. , and more preferably 〇" to 15 parts by weight. When a metal carboxylate (for example, rhodium, aluminum or zirconium) or an acetoacetone compound is used as a curing accelerator based on an organic metal, since the compatibility of the curing accelerator with the epoxy resin is poor, The transparency of the cured product may be impaired. In this case, the compatibility between the epoxy resin and the curing accelerator can be improved by adding a polyol compound (e.g., a diol (e.g., propylene glycol)) to the compound. The amount of the polyol compound (e.g., diol) is not specifically limited. It may be in parts by weight of the (10) parts by weight of the epoxy resin, 143089.doc • 12· 201016813. The adhesive composition may further comprise an antioxidant. The antioxidant has an effect of suppressing yellowing of the resin caused by oxidative degradation, and thus can be effectively used for optical applications such as semiconductor encapsulants and die bonding materials. The decrease in transparency caused by the initial yellowing can be suppressed by the addition of an antioxidant. Examples of the antioxidant include "Irgan〇x 1〇1〇" (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd., by Sumit〇 (10)

"Sumilizer GS" (trade name) manufactured by ChemiCal C〇., Ltd.

r Tinuvin 770DF" (trade name) manufactured by Ciba Specialty Chemicals Co" Ltd. The adhesive composition of the present disclosure may optionally include an additive. Examples of suitable additives include a filler (viscosity modifier) (for example, fine powdered silicone), a decane coupling agent (viscosity modifier) (for example, 7-glycidoxypropyltrimethoxydecane, "a-187" (trade name) manufactured by Nipp〇n❿丨C C〇mpany Limited) and an ultraviolet absorber (for example, manufactured by Chemical Co Ltd. under the trade name "Sumisorb 400"). The adhesive sword composition of the present disclosure can be used in various forms. Generally, it can be used in the form of a paste and can be applied to a joint portion or used for sealing after being taken out of the container at the time of use. The f-form can be applied by a bar coating method. The adhesive composition of the present invention can also be used as a sheet molding article. Processing performance can be improved by forming a sheet. The thickness of the sheet varies depending on factors such as the purpose and location, and is usually 50 to 200 μηη, preferably 8G to 12G (four). The sheet is usually formed by (4) molding into 143089.doc •13·201016813. Generally in this technical field, release paper (e.g., polyoxygenated paper) can be laminated to the resulting sheet adhesive composition. Further, the resulting sheet-like resin composition may be wound into a roll and then stored or shipped. The adhesive compositions of the present disclosure are stable at temperatures of from about 25 to 27 〇 ec and are useful in a variety of applications, particularly luminescent devices. Generally, a coating composition is used as a bonding material for a light-emitting device. The illumination device includes, but is not limited to, an LED wafer. A light-emitting diode device having an LED chip mounted therein is used, for example, in a lighting device and a signal device. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an adhesive composition using the present disclosure as a bonding material 1. Using the bonding material 丨, the light-emitting device 4 is bonded and mounted to the reflective layer 2. A reflective layer 2 is formed on the surface of the substrate 3. The reflective layer 2 can be made of a metal film such as a silver plated or silver vapor deposited film. The light-emitting device 4 can be coated with a sealing resin 5. For example, when the light-emitting device 1 is a light-emitting diode, the light-emitting device 4 is an LED chip. In the light-emitting device 1A, the light from the light-emitting 7G member 4 reaches the reflective layer 2 on the substrate via the transparent bonding material, and the light is reflected there, so that the light energy from the light-emitting element 4 can be effectively utilized. When the adhesive composition of the present disclosure is used as a bonding material of a light-emitting element (for example, an LED wafer), the light-emitting element must be fixed to, for example, a susceptor at a predetermined adhesive strength or higher, for the light-emitting element. Give the impact. In conventional adhesive compositions, it is difficult to achieve high adhesion strength on a reflective layer such as a silver plating layer. However, when the adhesive composition of the present invention is used, the adhesive strength of the adhesive composition can be increased to 6 MPa' and 8 MPa or more. 143089.doc 201016813 When the adhesive sword composition of the present disclosure is used as a wafer (e.g., LED wafer) bonding material, the transmitted light system is not colored so that the light energy is almost completely lost because of high transparency. When a cured product having a thickness of 0.2 mm is obtained from the adhesive composition, transparency of 95% or more can be achieved at 4 Torr to 5 〇〇 nm. The adhesive composition of the present disclosure can be used in optical display devices such as liquid crystal panels and plasma display panels to join or enclose members therein. Examples of other display devices include coffee (surface electric field display devices) and organic EL devices. Examples Examples 1 to 4 and Comparative Examples 1 to 6 The materials in the following Table 1 were mixed in each mixing ratio shown in Table 2 to prepare an adhesive composition.

143089.doc 15 201016813 Raw material manufacturer Daicel Chemical Industries Ltd. ADEKA CORPORATION New Japan Chemical Co., Ltd. New Japan Chemical Co., Ltd. NIHON KAGAKU SANGYO CO., LTD. s 'B (/3 1 lH 1 U White PL, 1 Q gs Q sg UBE INDUSTRIES, LTD. FUJI KASEIKOGYO C〇” LTD. 1 Dow Coming Toray Co” Ltd. 1 Ciba Specialty Chemicals Inc. Sumitomo Chemical Co., Ltd. Sumitomo Chemical Co.5 Ltd. Ciba Specialty Chemicals Inc. Sumitomo Chemical Co., Ltd. Cabot Corporation Common name 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexyl carboxylate hydrogenated double-peck glycidyl ether 4-methylhexahydrophthalic anhydride Hydrogenated methyl nadic acid anhydride 2-ethylhexanoic acid ethylene glycol 1,4-cyclohexane dimethanol diol j 1,6-hexanediol-based polycarbonate diol dicarboxylic acid modified polycarbonate Amidoxime-modified curing agent decane coupling agent|tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid]pentaerythritol Ί M5 〇Ί ^ ^^^ A « ^ \\ )179 r—^ 蚪曰Ϋ 5ί 3 w ^ w\ Η城: City·? cA 2 bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate 2,4-di-t-butylphenyl-3,5-di··second butyl _ 4-Benzene vinegar fine powdery silicone component epoxy resin anhydride anhydride anhydride curing accelerator curing accelerator compatibilizer carbonate compound carbonate compound carbonate compound curing accelerator viscosity improver antioxidant antioxidant I antioxidant Antioxidant UV absorber viscosity improver trade name CEL2021P 4080S MH-700G HNA-100 Zn Octoate Ethylene glycol UC-100 UH-100 Carbonate compound A FXR-1020 A-187 Irganox 1010 Sumilizer GS Sumilizer GP Tinuvin770DF Sumisorb 400 TS-720 143089.doc -16- 201016813 Example 14 〇〇o inch v〇卜 om 〇 inch example 13 〇o TH inch ub o cn O inch instance 12 〇〇<N o TH inch 〇o cn O inch instance 11 1 1 〇 〇<N oo cs 'Ο c5 <N inch example 10 1 〇〇in (N o rH inch ο 莫 寸 instance 9 〇〇CN o H inch 卜 〇 inch instance 8 _1 〇〇CN o inch 沄o 寸 寸 instance 7 〇〇CN o inch uo CN 卜 omo example 6 1 1 〇〇 (N o inch ub o cn 〇 inch example 5 _1 〇〇CN o inch o 卜 O 1-H inch instance 4 _1 〇 〇<N o 寸o o cn O inch example 3 〇〇(NT-H o inch m 〇o o iH inch example 2 〇〇o 卜 omo inch instance 1 1 〇〇... CN o inch v〇 inch 4080S CEL2021P MH -700G HNA-100 Zn Octoate 1 μ <L> fi α> 5 w FXR-1020 UC-100 < 1 ai UH-100 A-187 o TH r~HX ou £? hH Sumilizer GS Sumilizer GP Tinuvin770DF Sumisorb 400 TS-720 -17- 143089.doc 201016813 (<憋)<N< 1 Comparative Example 6 1 Ο Ο (Ν Ο I <d> mo 寸 contrast example 5 Ο ο 宕Η inch contrast example 4 CS Ο ^ -Η Ο ^-Η ο rN 卜o cn 〇 对比 对比 对比 对比 对比 3 3 3 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 寸 o 对比 对比 对比 对比 对比 对比 对比 对比 对比 对比 对比 对比 oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo 对比 对比 对比 对比 对比 对比 对比 对比 对比 对比η (Ν ψ·Ή Ο 1-Μ inch Inch 4080S CEL2021P MH-700G ΗΝΑ-100 Ζη Octoate 1 —丨― % τα α> § 1 PQ FXR-1020 UC-100 < =s 1 UH-100 A-187 〇o X o § Sumilizer GS Sumilizer GP Tinuvin770DF Sumisorb 400 TS-720 143089.doc -18- 201016813 "Carbonate compound A" (di-acid-modified polycarbonate) is a synthetic product having the following structure. [Chemical Formula 5]

φ R is hydrogen or fluorenyl. The carbonate compound A is prepared as follows. Polycarbonate diol (uc. 100, manufactured by Ube Industries, Ltd.) and dibasic anhydride (NH7 oxime, manufactured by New Japan Chemical Co., Ltd.) under stirring at room temperature together with triethylamine in toluene The reaction is carried out in a solvent. Then, the reaction solvent and the extraction solvent are removed by an evaporator. The structure of the product was confirmed to be the above structure using a nuclear magnetic resonance apparatus (NMR). Manufacture of Adhesive Samples • In a 1.1 1 (liter) tank, weigh the raw materials (listed in lt) and then mix and mix in a processing blender. The resulting adhesive sample was measured under the following conditions. Shear Bond Strength (OLSS) As a test piece for adhesives, a silver plated (3 to 5 μm) copper plate (CU00P) of size i 6 mm x 25 mm x 5{) mm was prepared. The surface of the test piece was degreased with methyl ethyl ketone (MEK), and the above-prepared adhesive sample was applied to the surface of the silver plating layer. At this time, the adhesive area was measured to have a size of 12.5 mm x 25 mm. The two pieces of the silver-coated test piece thus coated with the adhesive 143089.doc -19· 201016813 were laminated on the surface of the applied adhesive, and then the wafer was temporarily fixed. The resulting adhesive was cured in a 12 Torr oven for one hour and then cured at 15 Torr for 2 hours. After curing the adhesive, the resulting laminated material was placed in a tensile tester and the adhesion strength of the sheet was measured at a test rate of 5 mm/min. The results are shown in Tables 3 to 7. The adhesive sample (thickness of the adhesive layer: 0.2 mm) prepared on a glass plate having the above thickness of 1.2 to 1.5 mm was used, and the permeability was measured by a spectrophotometer 仏 400 at 800 to 340 nm. The penetration of the adhesive layer was measured by using a glass plate alone as a base line. In some cases, the permeability was measured after 500 hours of aging treatment at 15 〇{>c. 143089,doc 20· 201016813 ❿ ❿ 143089.doc Comparative example 2 〇in (N o Ο Ο m ο T—^ 寸 inch contrast example 1 We (N o inch inch example 3 〇o ▼-H ΓΛ 〇 ο 寸 inch example 2 〇〇rH CS t—H o ο ο ο Η 寸 实例 实例 实例 ο 'r-H in (N o inch resin (Cel2021P) acid Sf (MH700G) carbonate (UC-100) curing accelerator (ZnOctoate) resistance Oxidizer (Irganox 1010) Antioxidant (Sumilizer GS) Antioxidant (Sumilizer GP) UV absorber (Sumisorb 400) Ethylene glycol viscosity improver (TS720) -21 - σ\ On Inch On 10.6 卜τ-H ON inch Od 10.3 00 〇\ On Bu ό 寸 Os On 00 Os OLSS at 25°C (MPa) OLSS at 100°C (MPa) Initial penetration (%T) 400 nm 470 nm 201016813 inch< Comparative example 3 〇( ο ο ^-Η Ο cn cn o rH inch 1 instance 10 〇<Ν Ο ο οο m 〇rH inch example 9 Ο τ-Η CN ο ο o inch inch example 8 Ο CN Ο Ο τ—Η οο 〇 rTMH inch example 7 Ο CN <Ν Ο τ—Η οο 〇 寸 inch example 6 ο ο ^-Η τ—Η Ό τ«·Η Ο 卜 ο mo 寸 寸 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 MH700G) Carbonate (UC-100) ZnOctoate Antioxidant (Sumilizer GS) Antioxidant (Sumilizer GP) UV Absorption (Sumisorb 400) Ethylene Gum Improver (TS720) Ν.Α. NA | Ν. Α. | NA 1 10.5 14.5 ON ON 10.4 inch Ο On oo ON 10.6 11.7 On 〇\ 00 10.2 On o On 〇〇 10.3 〇〇Os On On 00 ON OO Os VO 10.2 00 ON OLSS at 25°C ( MPa) 2 S 〇衾ϋΟ 〇 initial penetration (%τ) 400 nm 470 nm desert 3⁄4 photo malaria Yti礤砘嫦s *手阳W瘗Ik#Φ崁锲赵^^锖^荽^ Bromo璩》4^苳驷玉架143089.doc •22· 201016813 lr»< Example 2 Ο in o Ο ΓΟ Ο Η 寸 inch example 12 ο ο CN VO o 卜 c5 m ο inch inch example 6 ο ο r_H rH o ο m ο Inch resin (Cel2021P) Anhydride (MH700G) Carbonate (UC-100) Carbonate (UH-100) Compound A Curing accelerator (ZnOctoate) Antioxidant Agent (Sumilizer GS) Antioxidant (Sumilizer GP) UV absorber (Sumisorb 400) Ethylene glycol viscosity improver (TS720) m 00 CS ON 00 ON Os od On oo Os oo On inch od 10.3 00 Os ON OLSS at 25 °C(MPa) OLSS at 10(TC(MPa) initial penetration (%T) 400 nm 470 nm 143089.doc -23- 201016813 9< Comparative Example 2 〇ο <·Η Ο ο rn o 1 〇r—Η CN 2 inch inch example 3 Ο ^-Η Ο ο ο m c> Example 2 Ο τ-^ Ο ο ο mo 寸 inch example 1 Ο (Ν ^Η ν〇Ο inch resin (Cel2021P) anhydride (MH700G Carbonate (UC-100) ZnOctoate Antioxidant (Sumilizer GS) Antioxidant (Sumilizer GP) UV absorber (Sumisorb 400) Ethylene glycol viscosity improver (TS720) as Os 00 in On m Bu Os § SS 10.6 11.7 On σ\ in os inch 10.6 10.3 00 〇\ σ\ On 00 inch ON σ\ 00 as § OO oo OLSS at 25°C (MPa) % P o δ CO 2 O Initial penetration (% T) 400 nm 470 nm Penetration after aging (% Τ) (150 degC, 500 h) 400 nm 470 nm 143089.doc -24- 201016813 1 Comparative example 6 I 〇〇Ο 卜 ο md inch contrast example 5 〇〇ο (Ν 寸 inch contrast example 4 | yn CN Ο ι~Η ο Ο ΓΛ 〇 —t-H inch inch example 14 in CN Ο ο Ο Ο cn 〇 inch inch example 13 〇^Η τ-Η ο οο m 〇 inch inch example 11 ο ο (Ν ^Η οο VO o CN CN inch example 6 ο ο <Ν ο ο ο m c> inch inch hydrogenated resin (4080S) aliphatic resin (CEL2021P Anhydride (MH-700G) Anhydride (ΗΝΑ-100) Curing accelerator (ZnOctoate) Amine curing accelerator r(FXR-1020) Carbonate (UC-100) Antioxidant (Sumilizer GS) Antioxidant (Sumilizer GP) Antioxidant (Tinuvin770DF) UV Absorber (Sumisorb 400) Ί 〇 Viscosity Improver (TS-720) cracked NANANANA 1 m 〇\ mo 〇\ 〇\ Light yellow inch in i> 00 Colorless (N cn od od o c- 〇\ C\ colorless od od 00 Os O^N colorless (NO od os 卜 ON colorless | 8.4 10.3 00 b c 〇 无 \ colorless OLSS at 25 ° C (MPa) OLSS at 100 ° C (MPa) initial penetration Sex (%T) 400 nm 470 nm initial color 143089.doc ·25· 201016813 DESCRIPTION FIG 1 is a single display adhesive compositions of the invention as a sectional view of a light emitting device of a sheet-like adhesive materials. [Description of main component symbols] 1 Bonding material 2 Reflective layer 3 Substrate 4 Light-emitting element 5 Sealing resin 10 Light-emitting device 143089.doc -26-

Claims (1)

201016813 VII. Patent Application Range: 1. An adhesive composition comprising an epoxy resin having no carbon-carbon unsaturated bond, an anhydride, a non-decomposable unsaturated bond, and an epoxy group. Or a carbonate compound of an acid anhydride-reactive group, and a curing accelerator' wherein the adhesive composition comprises 5 to 100 parts by weight of a carbonate compound based on 10 parts by weight of the epoxy resin. 2. The adhesive composition of claim 1, wherein the carbonate compound is represented by the following general formula (A): # [Chemical Formula 1] Wherein R1 represents a divalent hydrocarbon-containing group or a covalent bond; R2 each independently represents a monovalent smoke-containing group, and R3 represents a monovalent smoke-containing group or R4-X, wherein when R3 is a monovalent hydrocarbon-containing group, R3 is not Containing X, R4 represents a divalent hydrocarbon-containing group or a covalent bond 'and R1, R2, R3 and R4 have no carbon-carbon unsaturated bond; X represents a group reactive with an epoxy group or an acid anhydride; and η represents 1 Or a larger integer. 3. The adhesive composition of claim 2, wherein R3 is r4_x. An adhesive composition according to claim 2, wherein X is a carboxyl group, a hydroxyl group, an amine group or a thiol group. 5. The adhesive composition of claim 4, wherein R!, R2& R4 is an aliphatic group. 6. The adhesive composition of claim 5, wherein Ri, RW further comprises an ester group, a carbonate group or a guanamine group. The adhesive composition of claim 1, wherein the epoxy resin is an alicyclic epoxy compound or a hydrogenated epoxy compound. 8. The adhesive composition of the above-mentioned item 1, wherein the acid anhydride is non-aromatic and does not include a carbon-carbon unsaturated bond. The adhesive composition of claim 1, wherein the acid anhydride is a polycarboxylic acid anhydride. I. The adhesive composition of claim 1, which comprises 50 to 150 parts by weight of an acid anhydride and 1 to 2 parts by weight of a curing accelerator based on the oxime by weight of the epoxy resin. An adhesive composition further comprising an antioxidant. 12. A light-emitting device comprising a substrate, a light reflecting layer on the substrate, and an adhesive layer prepared from the adhesive composition of claim 1. a layer, and a light-emitting element, wherein the light-reflecting layer on the substrate is bonded to the light-emitting element through the adhesive layer. 13. The light-emitting device of claim 12, wherein the light-emitting element is a substrate and the light-emitting device is a light-emitting diode 14. An optical display device comprising a member joined using an adhesive composition as claimed in claim 1. 1430S9.doc