JP2009203423A - Adhesion improving oligomer for thermosetting organic/inorganic hybrid material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent adhesive/sealing material which does not cause adherends to undergo separation, cracking, etc., with a view to solve the problem that some transparent sealing materials used for encapsulating a solar cell element in a solar cell module and for encapsulating a light reception unit in optical communication, light-emitting diodes (LEDs), etc., some adhesives for bonding semiconductor packages to heat sinks, and the like are apt to suffer from defects such as interfacial delamination due to insufficient adhesion to substrates. <P>SOLUTION: Separation from an adherend due to a temperature change in post-processing and use and crack formation are prevented by performing heat sealing/bonding by using a base resin prepared by adding an oligomer obtained previously hydrolytically polycondensing an alkoxysilane containing an aromatic or aromatic-containing hydrocarbon group to an alkoxysilane as a raw material, mixing the mixture with an organic solvent, water, and an acidic catalyst, and heating the resultant mixture under agitation. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an oligomer added to a raw material and a method for producing the same in order to improve the adhesion of an organic-inorganic hybrid material.

    Transparent sealing materials used for sealing solar cell elements in solar cell modules, sealing light receiving parts for optical communication, sealing light emitting diodes (LEDs), adhesives between semiconductor packages and heat sinks, etc. Therefore, excellent adhesion to various substrates and adherends is required.

As the transparent sealing material, bisphenol A type epoxy resin is used as the main ingredient, and an acid anhydride is blended as a curing agent, ethylene / vinyl acetate copolymer and polyvinyl butyral having a high vinyl acetate content are used, In order to meet these strict requirements, attempts have been made to improve the composition and add ultraviolet absorbers, organic peroxides, and the like (for example, Patent Documents 1 to 3). An epoxy resin block-copolymerized with high heat-resistant silicone has also been developed.
JP 2006-066761 A JP 2003-228076 A Japanese Patent Laid-Open No. 10-253972

  Transparent sealing materials used for sealing solar cell elements in solar cell modules, sealing light receiving parts for optical communication, sealing light emitting diodes (LEDs), adhesives between semiconductor packages and heat sinks, etc. Some of them are prone to defects such as insufficient adhesion to the substrate and peeling of the interface.

  Silicone resins exhibit high transparency in the ultraviolet region, but have low adhesiveness, low strength, high moisture permeability (water absorption), and low refractive index. There are many challenges.

  An epoxy silicone having an epoxy group introduced with an epoxy group having high adhesiveness and high adhesiveness to a silicone resin having high ultraviolet transmittance has been developed.

  In other words, there is no transparent adhesive / sealing material that does not cause peeling or cracking on various adherends.

  The present invention provides an oligomer characterized by improving the adhesion of an organic-inorganic hybrid material by adding it to a raw material of a thermosetting organic-inorganic hybrid material, and a method for producing the same.

  In addition, the oligomer and the method for producing the same are characterized by having good compatibility with the raw material of the thermosetting organic-inorganic hybrid material.

  Further, in the above-mentioned oligomer and the method for producing the same, wherein the oligomer is uniformly dispersed in the raw material of the thermosetting organic-inorganic hybrid material and becomes part of the network when heated, or is present in the network as an inert substance is there.

  In addition, the oligomer and the method for producing the same are characterized by being produced by hydrolysis and polycondensation of an alkoxysilane containing an aromatic group or a hydrocarbon group containing an aromatic group.

  In addition, the oligomer having an average molecular weight of 2000 or less and the production method thereof.

  Moreover, it is said oligomer which melt | dissolves in an organic solvent, and its manufacturing method.

  Moreover, it is thermoplastic oligomer characterized by being thermoplastic, and its manufacturing method.

  Moreover, 100 times or less organic solvent, 1 or more times water, and 1 time or less acidic catalyst as a catalyst are added to the raw material alkoxysilane, and the mixed solution is heated at 50 to 200 ° C. for 10 minutes to 1 week. The oligomer and the method for producing the same as described above.

  By adding the oligomer of the present invention, it is possible to produce a transparent adhesive / sealing material that does not cause peeling or cracking on various adherends, which has been considered extremely difficult to produce so far. it can.

  The present invention relates to an oligomer characterized by improving the adhesion of an organic-inorganic hybrid material by adding it to a raw material of a thermosetting organic-inorganic hybrid material, and a method for producing the same. When used for sealing or bonding electronic parts, etc., peeling and cracking from the adherend due to temperature changes may cause defects such as poor appearance, poor contact, insufficient strength, and disconnection. It is necessary to have sufficient adhesion.

  Examples of the adherend include, but are not limited to, substrates such as glass, metal, plastic, ceramics, printed wiring substrates, and flexible substrates. Further, it is effective to improve the adhesion by applying a primer treatment to the adherend surface. Examples of the primer include, but are not limited to, synthetic rubber type, acrylic type, urethane type, epoxy type, silicone resin type, silane type, and amine type.

  Moreover, it is preferable that the oligomer has good compatibility with the raw material of the thermosetting organic-inorganic hybrid material. This is because when the compatibility is poor, the reaction tends to become non-uniform, and white turbidity and scattering occur in the organic-inorganic hybrid material.

  Further, it is preferable that the oligomer is uniformly dispersed in the raw material of the thermosetting organic-inorganic hybrid material and becomes a part of the network when heated, or exists in the network as an inactive substance. It is because it can exist stably in an organic-inorganic hybrid material.

  Moreover, it is preferable to produce an oligomer by hydrolyzing and polycondensing an alkoxysilane containing an aromatic or aromatic hydrocarbon group. Examples of the aromatic or aromatic hydrocarbon group include a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, and a naphthylmethyl group, and a phenyl group is particularly preferable.

  Moreover, it is preferable that the average molecular weight of an oligomer is 2000 or less. This is because when the average molecular weight exceeds 2000, the compatibility with the raw material of the thermosetting organic-inorganic hybrid material is deteriorated. A more preferable average molecular weight is 1000 or less.

  Moreover, it is preferable that an oligomer melt | dissolves in an organic solvent. This is because the solubility in the organic solvent improves the compatibility with the raw material of the thermosetting organic-inorganic hybrid material. Among organic solvents, it is particularly preferable to dissolve in alcohol. As alcohol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 1, 1 -Dimethyl-1-ethanol and the like, but may be a mixed solvent containing them.

  Moreover, it is preferable that an oligomer is thermoplastic. This is because, when the thermosetting organic-inorganic hybrid material contains a thermoplastic oligomer, it is possible to prevent peeling / cracking due to temperature change.

  Moreover, 100 times or less organic solvent, 1 or more times water, and 1 time or less acidic catalyst as a catalyst are added to the raw material alkoxysilane, and the mixed solution is heated at 50 to 200 ° C. for 10 minutes to 1 week. Thus, it is preferable to produce an oligomer.

  The reason for determining each addition amount is as follows.

  This is because when the amount of the organic solvent added is more than 100 times, the synthesis time is long, and industrial advantages such as productivity are small. Examples of the organic solvent include, but are not limited to, alcohol, acetone, tetrahydrofuran, dimethyl sulfoxide, N, N-dimethylformamide and the like.

  This is because when the amount of water added is less than 1 time, the hydrolysis reaction does not proceed sufficiently and unreacted alkoxy groups remain.

  This is because when the addition amount of the acidic catalyst is more than 1 time, phase separation is easy and a uniform cured body cannot be obtained.

  In the synthesis of an organic-inorganic hybrid material by a sol-gel method, an acidic catalyst is often used. However, for example, an electrode of an electronic material may be corroded by a catalyst residue in the obtained sealing material. May need to be removed.

  The acid can be removed by a liquid separation operation. The product obtained by reacting the raw material alkoxysilane is diluted with a non-polar organic solvent that is compatible with the product and is immiscible with water, and further mixed with pure water and stirred vigorously. It is possible to later remove the acid along with the aqueous layer. The nonpolar organic solvent can be removed by distillation under reduced pressure.

  Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, acetic acid, formic acid, maleic acid, fumaric acid, propionic acid, adipic acid, oleic acid, stearic acid, linoleic acid, benzoic acid and other organic acids. Acetic acid is particularly desirable. Other catalysts include metal alkoxides such as sodium methylate. However, the hydrolysis yield is low, and alkoxide tends to remain in the main agent. Since the alkoxide has low heat resistance, it tends to reduce the heat resistance of the organic-inorganic hybrid material.

  Examples of the nonpolar organic solvent used for the liquid separation operation include, but are not limited to, diethyl ether, xylene, toluene, chloroform, ethyl acetate, and isobutyl acetate.

  The reason for determining the synthesis conditions is as follows.

  This is because when the synthesis temperature of the oligomer is lower than 50 ° C., the synthesis time is long, and industrial advantages such as productivity are small. On the other hand, when the synthesis temperature of the oligomer is higher than 200 ° C., an oligomer having a desired composition cannot be obtained due to boiling of the mixed solution or evaporation of the raw material alkoxysilane.

  This is because when the synthesis time of the oligomer is shorter than 10 minutes, the hydrolysis / polycondensation reaction does not proceed sufficiently. On the other hand, when the oligomer synthesis time is longer than one week, the synthesis time becomes long, and industrial advantages such as productivity are small. The synthesis of the oligomer may be performed in an open system, may be performed in an inert atmosphere, or may be performed under reflux.

  Hereinafter, description will be made based on examples.

(Preparation of oligomer I)
At room temperature, 3 g of phenyltrimethoxysilane, 33 g of diphenyldimethoxysilane, 135 g of water, 69 g of ethanol and 900 mg of glacial acetic acid were mixed. The mixed solution was heated and stirred at 60 ° C. for 3 hours in an open system, and then heated and stirred at 180 ° C. for 2.5 hours to obtain a colorless and transparent viscous material. This viscous material was dissolved in diethyl ether, and acetic acid was extracted with pure water. After extraction, diethyl ether was distilled off to obtain oligomer I which was a colorless and transparent viscous material. The average molecular weight of the oligomer I was 800, and it was soluble in organic solvents such as alcohol. Moreover, it became hard when cooled, and was found to exhibit thermoplasticity due to its viscosity near room temperature.

(Preparation of sealing sample)
When an ethanol solution of oligomer I was added to phenyltrimethoxysilane and dimethyldimethoxysilane, which are raw materials for thermosetting organic-inorganic hybrid materials, it was found that the solution was colorless and transparent and had good compatibility. Next, water and an acid catalyst were added to the ethanol solution, and the mixture was heated and stirred. A colorless and transparent viscous liquid was obtained by the progress of hydrolysis and polycondensation reaction, which was dissolved in diethyl ether, and the acid catalyst was extracted with pure water. Diethyl ether was distilled off to obtain a colorless and transparent viscous liquid (hereinafter referred to as main agent). Dibutyltin diacetate was added to the main agent, applied to a float glass substrate, and heated at 60 ° C. for 3 hours, at 100 ° C. for 3 hours, and at 150 ° C. for 5 hours to prepare a sealed sample. No optical scattering or cloudiness was observed in this sealed sample, and since it was insoluble in an alcohol solvent, the oligomer was uniformly in the sealing material as part of the network or as an inert substance. I found that it existed. Moreover, a thermal cycle test (conforming to JIS C 0025) at −40 ° C. to 100 ° C. and a solder heat resistance test (conforming to JIS C 60068-2-20) at 260 ° C. for 10 seconds are performed on the sealed sample. As a result, no peeling or cracking occurred.

(Preparation of oligomer II)
At room temperature, 3 g of phenyltrimethoxysilane, 33 g of diphenyldimethoxysilane, 135 g of water, 69 g of dimethyl sulfoxide, and 900 mg of glacial acetic acid were mixed. The mixed solution was heated and stirred in a closed system at 60 ° C. for 3 hours, and then heated and stirred under reflux for 2.5 hours. After completion of the reaction, diethyl ether was added and acetic acid was extracted with pure water. After the extraction, diethyl ether was distilled off, and the mixture was further heated at 200 ° C. for 1 hour to allow the reaction to proceed to obtain oligomer II which was a colorless and transparent viscous material. The average molecular weight of the oligomer II was 800, and it was soluble in organic solvents such as alcohol. Moreover, it became hard when cooled, and it was found to show thermoplasticity because of its viscosity near room temperature.

(Preparation of sealing sample)
When an ethanol solution of oligomer II was added to phenyltrimethoxysilane and dimethyldimethoxysilane, which are raw materials for thermosetting organic-inorganic hybrid materials, it was found that the solution was colorless and transparent and had good compatibility. Next, water and an acid catalyst were added to the ethanol solution, and the mixture was heated and stirred. A colorless and transparent viscous liquid was obtained by the progress of hydrolysis and polycondensation reaction, which was dissolved in diethyl ether, and the acid catalyst was extracted with pure water. Diethyl ether was distilled off to obtain a colorless and transparent main agent. Dibutyltin diacetate was added to the main agent, applied to a commercially available printed circuit board made of plastic, and heated at 60 ° C. for 3 hours, at 100 ° C. for 3 hours, and at 150 ° C. for 5 hours to prepare a sealed sample. No optical scattering or cloudiness was observed in this sealed sample, and since it was insoluble in an alcohol solvent, the oligomer was uniformly in the sealing material as part of the network or as an inert substance. I found that it existed. Moreover, a thermal cycle test (conforming to JIS C 0025) at −40 ° C. to 100 ° C. and a solder heat resistance test (conforming to JIS C 60068-2-20) at 260 ° C. for 10 seconds are performed on the sealed sample. As a result, no peeling or cracking occurred.

(Preparation of oligomer III)
At room temperature, 4 g of 1-naphthyltrimethoxysilane, 33 g of diphenyldimethoxysilane, 135 g of water, 69 g of ethanol, and 900 mg of glacial acetic acid were mixed. The mixed solution was heated and stirred at 60 ° C. for 3 hours in an open system, and then heated and stirred at 180 ° C. for 2.5 hours to obtain a colorless and transparent viscous material. This viscous material was dissolved in diethyl ether, and acetic acid was extracted with pure water. After extraction, diethyl ether was distilled off to obtain oligomer III, a colorless and transparent viscous material. The average molecular weight of the oligomer III was 800, and it was soluble in organic solvents such as alcohol. Moreover, it became hard when cooled, and was found to exhibit thermoplasticity due to its viscosity near room temperature.

(Preparation of sealing sample)
When an ethanol solution of oligomer III was added to phenyltrimethoxysilane and dimethyldimethoxysilane, which are raw materials for thermosetting organic-inorganic hybrid materials, it was found that the solution was colorless and transparent and had good compatibility. Next, water and an acid catalyst were added to the ethanol solution, and the mixture was heated and stirred. A colorless and transparent viscous liquid was obtained by the progress of hydrolysis and polycondensation reaction, which was dissolved in diethyl ether, and the acid catalyst was extracted with pure water. Diethyl ether was distilled off to obtain a colorless and transparent main agent. Dibutyltin diacetate is added to the base material, applied to a commercially available flexible substrate that has been surface-treated with an amine primer in advance, and heated at 60 ° C. for 3 hours, at 100 ° C. for 3 hours, and at 150 ° C. for 5 hours to provide a sealed sample Was made. No optical scattering or cloudiness was observed in this sealed sample, and since it was insoluble in an alcohol solvent, the oligomer was uniformly in the sealing material as part of the network or as an inert substance. I found that it existed. Moreover, a thermal cycle test (conforming to JIS C 0025) at −40 ° C. to 100 ° C. and a solder heat resistance test (conforming to JIS C 60068-2-20) at 260 ° C. for 10 seconds are performed on the sealed sample. As a result, no peeling or cracking occurred.

(Preparation of oligomer IV)
At room temperature, 4 g of 1-benzyltrimethoxysilane, 33 g of diphenyldimethoxysilane, 135 g of water, 69 g of ethanol and 900 mg of glacial acetic acid were mixed. The mixed solution was heated and stirred at 60 ° C. for 3 hours in an open system, and then heated and stirred at 180 ° C. for 2.5 hours to obtain a colorless and transparent viscous material. This viscous material was dissolved in diethyl ether, and acetic acid was extracted with pure water. After extraction, diethyl ether was distilled off to obtain oligomer IV, a colorless and transparent viscous material. The average molecular weight of the oligomer IV was 800 and was soluble in organic solvents such as alcohol. Moreover, it became hard when cooled, and was found to exhibit thermoplasticity due to its viscosity near room temperature.

(Preparation of sealing sample)
When an ethanol solution of oligomer IV was added to phenyltrimethoxysilane and dimethyldimethoxysilane, which are raw materials for thermosetting organic-inorganic hybrid materials, it was found that the solution was colorless and transparent and had good compatibility. Next, water and an acid catalyst were added to the ethanol solution, and the mixture was heated and stirred. A colorless and transparent viscous liquid was obtained by the progress of hydrolysis and polycondensation reaction, which was dissolved in diethyl ether, and the acid catalyst was extracted with pure water. Diethyl ether was distilled off to obtain a colorless and transparent main agent. Dibutyltin diacetate is added to the base material and applied to a commercially available plastic printed wiring board that has been surface-treated with a silane primer in advance, heated at 60 ° C. for 3 hours, 100 ° C. for 3 hours, and 150 ° C. for 5 hours. A sealed sample was produced. No optical scattering or cloudiness was observed in this sealed sample, and since it was insoluble in an alcohol solvent, the oligomer was uniformly in the sealing material as part of the network or as an inert substance. I found that it existed. Moreover, a thermal cycle test (conforming to JIS C 0025) at −40 ° C. to 100 ° C. and a solder heat resistance test (conforming to JIS C 60068-2-20) at 260 ° C. for 10 seconds are performed on the sealed sample. As a result, no peeling or cracking occurred.

(Preparation of oligomer V)
At room temperature, 3 g of 1-phenethyltrimethoxysilane, 33 g of diphenyldimethoxysilane, 135 g of water, 69 g of ethanol, and 900 mg of glacial acetic acid were mixed. The mixed solution was heated and stirred at 60 ° C. for 3 hours in an open system, and then heated and stirred at 180 ° C. for 2.5 hours to obtain a colorless and transparent viscous material. This viscous material was dissolved in diethyl ether, and acetic acid was extracted with pure water. After extraction, diethyl ether was distilled off to obtain oligomer V which was a colorless and transparent viscous material. The average molecular weight of the oligomer V was 800, and it was soluble in organic solvents such as alcohol. Moreover, it became hard when cooled, and was found to exhibit thermoplasticity due to its viscosity near room temperature.

(Preparation of sealing sample)
When an ethanol solution of oligomer V was added to phenyltrimethoxysilane and dimethyldimethoxysilane, which are raw materials for thermosetting organic-inorganic hybrid materials, it was found that the solution was colorless and transparent and had good compatibility. Next, water and an acid catalyst were added to the ethanol solution, and the mixture was heated and stirred. A colorless and transparent viscous liquid was obtained by the progress of hydrolysis and polycondensation reaction, which was dissolved in diethyl ether, and the acid catalyst was extracted with pure water. Diethyl ether was distilled off to obtain a colorless and transparent main agent. Dibutyltin diacetate was added to the main agent, applied to a commercially available flexible substrate, and heated at 60 ° C. for 3 hours, at 100 ° C. for 3 hours, and at 150 ° C. for 5 hours to prepare a sealed sample. No optical scattering or cloudiness was observed in this sealed sample, and since it was insoluble in an alcohol solvent, the oligomer was uniformly in the sealing material as part of the network or as an inert substance. I found that it existed. Moreover, a thermal cycle test (conforming to JIS C 0025) at −40 ° C. to 100 ° C. and a solder heat resistance test (conforming to JIS C 60068-2-20) at 260 ° C. for 10 seconds are performed on this sealed sample. As a result, no peeling or cracking occurred.

(Comparative Example 1)
It applied to the commercially available plastic printed wiring board using the silicone resin marketed for sealing and adhesion | attachment, and produced the sealing sample. A thermal cycle test (conforming to JIS C 0025) at −40 ° C. to 100 ° C. and a solder heat resistance test (conforming to JIS C 60068-2-20) at 260 ° C. for 10 seconds were performed on this sealed sample. All the peelings and cracks occurred.

(Comparative Example 2)
(Preparation of oligomer A)
At room temperature, 3 g of phenyltrimethoxysilane, 35 g of 3-glycidyloxypropyl (dimethoxy) methylsilane (molecular weight 220), 135 g of water, 70 g of ethanol, and 9 mg of glacial acetic acid were mixed. The mixed solution was heated and stirred at 60 ° C. for 3 hours in an open system, and then heated and stirred at 180 ° C. for 3 hours to obtain an oligomer A. Oligomer A was insoluble in organic solvents and the molecular weight could not be measured. Moreover, the oligomer A did not show thermoplasticity.

An attempt was made to produce the main agent using the oligomer A in the same procedure as in Example 1, but the compatibility was poor and it was opaque. Further sealing was attempted, but cracking and peeling occurred during heat curing.
(Comparative Example 3)
(Preparation of oligomer B)
At room temperature, 3 g of methyltrimethoxysilane, 30 g of both-end silanol dimethyl silicone (commercial product, molecular weight 18000), 20 g of water, 69 g of ethanol, and 2 mg of glacial acetic acid were mixed. The mixed solution was heated and stirred at 60 ° C. for 2 hours in an open system, and then heated and stirred at 180 ° C. for 3 hours to obtain an oligomer B. The average molecular weight of the oligomer B was 25000 and showed thermoplasticity.

  The preparation of the main agent was attempted using the oligomer B in the same procedure as in Example 1, but the compatibility was poor and it was opaque. Further sealing was attempted, but it remained opaque after curing.

  Sealing of semiconductor light emitting elements such as light emitting diodes (LEDs) used for backlights, display boards, displays, various indicators, sealing of solar cell elements in solar cell modules, sealing of light receiving parts for optical communication It can be used for the transparent sealing material used for the semiconductor etc., the adhesive agent of a semiconductor package and a heat sink, etc. In addition, materials for sealing and covering display components such as PDP, optical information communication device materials such as optical switches and optical couplers, optical equipment materials, optical functional (non-linear) optical materials, adhesive materials, etc. It can be used in fields where low melting glass is used, and fields where organic materials such as epoxy are used.

Claims (8)

An oligomer characterized by improving the adhesion of an organic-inorganic hybrid material by adding it to a raw material of a thermosetting organic-inorganic hybrid material, and a method for producing the same. The oligomer according to claim 1 and a method for producing the same according to claim 1, which have good compatibility with a raw material of a thermosetting organic-inorganic hybrid material. The oligomer according to claim 1 or 2, which is uniformly dispersed in the raw material of the thermosetting organic-inorganic hybrid material and becomes part of the network when heated, or exists in the network as an inert substance. Its manufacturing method. The oligomer according to any one of claims 1 to 3, which is prepared by hydrolysis and polycondensation of an alkoxysilane containing an aromatic or aromatic hydrocarbon group. The oligomer according to any one of claims 1 to 4, wherein the average molecular weight is 2000 or less, and a method for producing the oligomer. The oligomer according to any one of claims 1 to 5 and a method for producing the same, which are dissolved in an organic solvent. The oligomer according to any one of Claims 1 to 6, which is thermoplastic, and a method for producing the same. Add 100 times or less organic solvent, 1 or more times water, and 1 or less times acidic catalyst as a catalyst to the raw material alkoxysilane, and heat the mixed solution at 50 to 200 ° C. for 10 minutes to 1 week. The oligomer according to any one of claims 1 to 7 and a method for producing the same.