JP4502676B2 - POLYMER MANUFACTURING METHOD AND POLYMER MATERIAL - Google Patents

Description

  The present invention relates to a method for producing a polymer with extremely little residual unreacted monomer component, and a material and member using the polymer.

  A member using a polymer such as plastic or rubber is light and inexpensive and easy to handle. Therefore, it is used in a large amount in daily life and every industry.

  However, the gas volatilized from these polymers has recently become a problem. Gases evaporating from building materials and automobiles in daily life are said to be the cause of allergic diseases such as atopic dermatitis, which is said to be a modern disease.

  In addition, in the manufacturing process of semiconductor devices, flat panel display devices, etc., the presence of volatile components from the polymer used greatly affects device performance, causing a reduction in productivity and reliability.

  There are various gases that volatilize from such polymers, such as additives and residual solvents. Among them, the residual low molecular weight polymer, particularly residual unreacted monomer components, is the main component of the volatile gas and has an adverse effect. The main factor. In order to eliminate these residual unreacted monomer components, it is conceivable to remove them by some method after the polymerization reaction or to eliminate the reaction by completing the reaction during the polymerization reaction.

  Various methods for removing residual unreacted monomer components after the polymerization reaction have been reported.

  First, high-temperature baking and decompression treatment that have been performed for a long time have some effects. However, this method cannot be completely removed, and it is not economical because a large device needs to be prepared for a large member.

  Further, for example, according to Patent Document 1 and Patent Document 2, the polymer is brought into contact with fine inert gas bubbles generated by a disperser or ultrasonic irradiation in a hot water tank, and the volatile substance in the polymer is removed. In the method of removing and the method of removing the volatile substance contained in the molded polymer, the polymer is irradiated (applied) with ultrasonic waves while directly contacting the polymer with the cleaning liquid, and the volatile substance is removed. A method of removal is described.

  By using this method, it is possible to reduce volatile substances, but it is impossible to completely remove monomer components that often require a large amount of energy for volatilization.

JP 7-258331 A Japanese Patent Laid-Open No. 7-216115

  The present invention has been made by paying attention to the above circumstances, and the technical problem thereof is a method for producing a polymer with very little residual unreacted monomer component, which has been difficult to remove, and a material using the polymer. And providing a member.

  The gist of the polymer production method according to the present invention that solves the above-mentioned problems is that the residual unreacted monomer in the polymer is extremely reduced.

  That is, according to the present invention, in a method for producing a polymer comprising a step of polymerizing the monomer by applying energy such as heat or light to the monomer, the monomer under reaction during the reaction or after the reaction, A method for producing a polymer is obtained, wherein megasonic is directly applied to the polymer or the polymer produced by the reaction. It is preferred to degas the gaseous component in the monomer.

  Moreover, according to this invention, the manufacturing method of the polymer characterized by applying megasonic directly to the polymer obtained by the block polymerization method is obtained.

  According to the present invention, in the method for producing a polymer, comprising a step of molding a polymer dissolved in a solvent by coating or the like, and a step of heating the molded polymer to remove the solvent. A method for producing a polymer is obtained, wherein megasonic is directly applied to the polymer while at least a part of the polymer is removed or after the solvent is removed.

  Further, according to the present invention, in any one of the methods for producing a polymer, the polymerization reaction for obtaining the polymer is performed under reduced pressure or in an inert gas atmosphere having a water concentration and an oxygen concentration of 1 ppm or less, respectively. Or the application of the megasonic is performed under reduced pressure or in an inert gas atmosphere having a water concentration and an oxygen concentration of 1 ppm or less, respectively.

  Moreover, according to this invention, in the manufacturing method of any one said polymer, the frequency of the megasonic used is 0.1 MHz-100 MHz, The manufacturing method of the polymer characterized by the above-mentioned is obtained.

  Moreover, according to this invention, the semiconductor sealing material characterized by consisting essentially of the polymer manufactured using the said any one manufacturing method of a polymer is obtained.

  Further, according to the present invention, the polymer produced by using any one of the polymer production methods is used for at least a part of at least one of the substrate and the interlayer insulating film. A wiring board is obtained.

  Further, according to the present invention, a semiconductor device, a flat panel display device, in which a wiring layer is formed using at least a part of the interlayer insulating film using the polymer produced by any one of the polymer producing methods, Electronic devices such as computers and mobile phone terminals can be obtained.

  Moreover, according to this invention, the transparent photosensitive material characterized by consisting essentially of the polymer manufactured using the said any one manufacturing method of a polymer is obtained.

  In addition, according to the present invention, there is obtained an optical fiber characterized in that it consists essentially of a polymer produced by using any one of the aforementioned polymer production methods.

  In addition, according to the present invention, an optical device using a polymer produced by using any one of the polymer production methods described above as at least a part of an optical waveguide can be obtained.

  In addition, according to the present invention, there is obtained a polymer material for covering an electric wire / wiring cable, which is substantially composed of a polymer produced by using any one of the aforementioned polymer production methods.

  Moreover, according to this invention, the polymeric material for construction characterized by consisting essentially of the polymer manufactured using the manufacturing method of any one said polymer is obtained.

  Moreover, according to this invention, the medical polymer material characterized by consisting essentially of the polymer manufactured using the said any one manufacturing method of a polymer is obtained.

  Moreover, according to this invention, the polymer material for foodstuffs characterized by consisting essentially of the polymer manufactured using the said any one manufacturing method of a polymer is obtained.

  Furthermore, according to the present invention, the polymer for automobiles, ships, airplanes, rockets, or space vehicles, characterized in that it substantially comprises a polymer produced by using any one of the above-mentioned polymer production methods. A member is obtained.

  According to the present invention, a polymer containing very little residual unreacted monomer component can be produced by directly irradiating (applying) megasonic to a polymer containing residual unreacted monomer. If this is carried out in an atmosphere free of oxygen and moisture, the effect is further remarkable.

  The present invention will be described in more detail.

  In the present invention, the residual unreacted monomer having a low molecular weight is activated when the polymer is polymerized or by directly irradiating the polymer polymerized to some extent with megasonic. The residual unreacted monomer activated by the megasonic has a high collision frequency and becomes more reactive.

  Even if the residual unreacted monomer is localized, since the megasonic activates the monomer in a directional manner, the reaction can proceed without deteriorating the polymer.

  Further, when there are a lot of unreacted monomers, that is, in a liquid state, the gas component dissolved in the system attenuates the effect of megasonic, so it is preferable to degas before the reaction.

  In the atmosphere to be reacted, if there is a highly reactive atmosphere such as moisture or oxygen, side reactions such as decomposition of the polymer will occur, or the monomer will react and become inactive. It is preferable to carry out below.

  The present inventors have found that the residual unreacted monomer that becomes a volatile component is activated by megasonics, find out that it reacts even in a localized state in the solid, and have arrived at the present invention. Is.

Te present invention smell, the main Gasonikku, among ultrasound, referred to as high frequency, the megasonic is irradiated directly to the reaction system. The megasonic frequency is preferably 0.1 to 100 MHz, more preferably 0.5 to 10 MHz, and still more preferably 0.8 to 5 MHz.

  Moreover, as for the megasonic irradiation method, for example, it is preferable to install a megasonic oscillation device directly under a polymer placed in a container.

  The reaction system should be as close as possible to the megasonic oscillation device, and the shape of the polymer is preferably flat.

  If the polymer is a foam or hollow, the megasonic effect is weakened, which is not preferable.

  When the monomer is polymerized, degassing increases the megasonic effect.

  As a degassing method, a method of reducing the pressure of the entire reaction system is preferable. By slightly heating, the viscosity of the reaction system is lowered, so that the degassing becomes easier.

  When a polymer dissolved in a solvent is molded by coating or the like, it is preferable to directly irradiate megasonic after removing the solvent to some extent by heating.

  When water or oxygen is present in the reaction system, the megasonic effect is weakened, so the reaction atmosphere is preferably in a vacuum or under an inert gas.

  The water and oxygen concentrations in the reaction atmosphere are each preferably 1 ppm or less, more preferably 100 ppb or less, and even more preferably 10 ppb or less.

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples.

(Example 1)
Mix well with bisphenol A type epoxy resin and hexamethylene diamine as a curing agent, apply it on a quartz plate to a thickness of 1 micron, place it on a megasonic oscillator, put it in a sealed container and depressurize the system, After degassing, an inert gas was introduced, purge was performed under reduced pressure, the water and oxygen in the system were reduced to 1 ppm or less, and then heat-baked at 100 ° C. for 5 hours while irradiating megasonic with a frequency of 1 MHz.

  After the treatment, the monomer component that volatilizes from the polymer is volatilized at 100 ° C. in a high-purity argon stream with a moisture and oxygen concentration of 1 ppb or less, and examined with an atmospheric pressure ionization plasma mass spectrometer. It was the following.

(Example 2)
Mix well with bisphenol A type epoxy resin and hexamethylene diamine as a curing agent, apply it on a quartz plate to a thickness of 1 micron, place it on a megasonic oscillator, put it in a sealed container and depressurize the system, After deaeration, an inert gas is introduced, purge is performed under reduced pressure, the moisture and oxygen in the system is reduced to 1 ppm or less, and then heated and baked at 100 ° C. for 5 hours, and then at 100 ° C. for 30 minutes at 1 MHz. Megasonic irradiation was performed.

  After the treatment, the monomer component that volatilizes from the polymer is volatilized at 100 ° C. in a high-purity argon stream with a moisture and oxygen concentration of 1 ppb or less, and examined with an atmospheric pressure ionization plasma mass spectrometer. It was the following.

(Example 3)
After placing a polycarbonate plate having a thickness of 1 mm with a residual monomer volatile component of 1% or more based on the weight of the polymer on a megasonic oscillator with a frequency of 1 MHz, placing it in a sealed container, depressurizing the system, and degassing, An inert gas was introduced, purged under reduced pressure, the water and oxygen in the system were reduced to 1 ppm or less, and irradiation was performed at 100 ° C. for 30 minutes.

  After the treatment, the monomer component volatilized from the polymer was volatilized at 100 ° C. in a high-purity argon stream having a moisture and oxygen concentration of 1 ppb or less, and examined with an atmospheric pressure ionization plasma mass spectrometer. Met.

(Example 4)
After applying a polyimide prepolymer (polyamic acid) dissolved in a solvent on a quartz plate to a thickness of 1 micron, placing it on a megasonic oscillator, putting it in a sealed container, depressurizing the system, and degassing, Inert gas was introduced, purge was performed under reduced pressure, the water and oxygen in the system were reduced to 1 ppm or less, and then heat-baked at 300 ° C. for 5 hours while irradiating megasonic with a frequency of 1 MHz.

  After the treatment, the monomer component that volatilizes from the polymer is volatilized at 100 ° C. in a high-purity argon stream with a moisture and oxygen concentration of 1 ppb or less, and examined with an atmospheric pressure ionization plasma mass spectrometer. It was the following.

(Example 5)
After applying polyimide prepolymer (polyamic acid) dissolved in a solvent on a quartz plate to a thickness of 1 micron, placing it on a megasonic oscillator, putting it in a sealed container, depressurizing the system, and degassing, An inert gas was introduced and purged under reduced pressure to reduce the moisture and oxygen in the system to 1 ppm or less, followed by heating and baking at 300 ° C. for 5 hours, and then irradiation with megasonic with a frequency of 1 MHz for 30 minutes.

  After the treatment, the monomer component that volatilizes from the polymer is volatilized at 100 ° C. in a high-purity argon stream with a moisture and oxygen concentration of 1 ppb or less, and examined with an atmospheric pressure ionization plasma mass spectrometer. It was the following.

(Comparative Example 1)
Mix well with bisphenol A type epoxy resin and hexamethylenediamine as a curing agent, apply it on a quartz plate to a thickness of 1 micron, put it in a sealed container, depressurize the inside of the system, deaerate it, An active gas was introduced, purge was performed under reduced pressure, the water and oxygen in the system were reduced to 1 ppm or less, and then heat-baked at 100 ° C. for 5 hours (without megasonic irradiation).

  After the treatment, the monomer component that volatilizes from the polymer is volatilized at 100 ° C. in a high-purity argon stream having a moisture and oxygen concentration of 1 ppb or less, and examined by an atmospheric pressure ionization plasma mass spectrometer. % Or more.

(Comparative Example 2)
Bisphenol A type epoxy resin and hexamethylene diamine as a curing agent are mixed well, applied on a quartz plate to a thickness of 1 micron, and in a normal atmosphere with a humidity of 50% or higher without degassing etc. And baking at 100 ° C. for 5 hours. (No megasonic irradiation).

  After the treatment, the monomer component that volatilizes from the polymer is volatilized at 100 ° C. in a high-purity argon stream having a moisture and oxygen concentration of 1 ppb or less, and examined by an atmospheric pressure ionization plasma mass spectrometer. % Or more.

(Comparative Example 3)
After placing a polycarbonate plate having a thickness of 1 mm with a residual monomer volatile component of 1% or more based on the weight of the polymer on a megasonic oscillator with a frequency of 1 MHz, placing it in a sealed container, depressurizing the system, and degassing, Inert gas was introduced, purge was performed under reduced pressure, the moisture and oxygen in the system were reduced to 1 ppm or less, and then megasonic was not irradiated, and heating was only performed at 100 ° C. for 30 minutes.

  After the treatment, the monomer component that volatilizes from the polymer is volatilized at 100 ° C. in a high-purity argon stream having a moisture and oxygen concentration of 1 ppb or less, and examined by an atmospheric pressure ionization plasma mass spectrometer. % Or more.

(Comparative Example 4)
A 1 mm thick polycarbonate plate having a residual monomer volatile component of 1% or more based on the weight of the polymer was placed in warm water at 80 ° C. and continuously irradiated with a 20 MHz ultrasonic oscillator for 1 hour.

  After the treatment, the monomer component that volatilizes from the polymer is volatilized at 100 ° C. in a high-purity argon stream having a moisture and oxygen concentration of 1 ppb or less, and examined by an atmospheric pressure ionization plasma mass spectrometer. % Or more.

(Comparative Example 5)
After applying polyimide prepolymer (polyamic acid) dissolved in a solvent on a quartz plate to a thickness of 1 micron, placing it on a megasonic oscillator, putting it in a sealed container, depressurizing the system, and degassing, Inert gas was introduced, purge was performed in a reduced pressure batch, water / oxygen in the system was reduced to 1 ppm or less, and then megabaked at 300 ° C. for 5 hours without being subjected to megasonic irradiation.

  After the treatment, the monomer components that volatilize from the polymer were volatilized at 100 ° C. in a high-purity argon stream with a moisture and oxygen concentration of 1 ppb or less, and examined with an atmospheric pressure ionization plasma mass spectrometer. It was 1% or more.

  As described above, since the polymer obtained by the method for producing a polymer according to the embodiment of the present invention does not contain a monomer component in the polymer, a semiconductor encapsulant in semiconductor production, a printed board, Interlayer insulation film, transparent photosensitive material, optical fiber used for optical communication, optical / electrical / communication materials such as optical waveguides, electronic / electrical / communication materials such as coating materials for electric / electric wires / wiring cables, building materials, medical use It can be used for materials using polymers in various fields such as materials, food materials, automobiles, ships, airplanes, and rocket members.

The method for producing a polymer according to the present invention includes a semiconductor encapsulant, a printed board, an interlayer insulating film, a transparent photosensitive material, an optical fiber, an optical waveguide, and a wire / wiring cable coating because the polymer does not contain a monomer component. It is applied to polymer materials in various fields such as materials, building materials, medical materials, food materials, automobiles, ships, airplanes and rocket members.

Claims (18)

  In a method for producing a polymer comprising a step of polymerizing a monomer by applying energy to the monomer, megasonic is directly applied to the monomer or polymer during the reaction or after the reaction or to the polymer produced by the reaction. And a method for producing a polymer.   The method for producing a polymer according to claim 1, further comprising a step of degassing a gas component in the monomer before the polymerization reaction step.   A method for producing a polymer, wherein megasonic is directly applied to a polymer obtained by a bulk polymerization method.   In a method for producing a polymer comprising a step of molding a polymer dissolved in a solvent and a step of heating the molded polymer to remove the solvent, during the removal of at least a part of the solvent or the solvent A method for producing a polymer, wherein megasonic is directly applied to the polymer after removal.   The method for producing a polymer according to any one of claims 1 to 4, wherein the polymerization reaction for obtaining the polymer is performed under reduced pressure or an inert gas atmosphere having a water concentration and an oxygen concentration of 1 ppm or less, respectively. A process for producing a polymer, characterized in that it is carried out below.   The method for producing a polymer according to any one of claims 1 to 5, wherein the application of the megasonic is performed under reduced pressure or in an inert gas atmosphere having a water concentration and an oxygen concentration of 1 ppm or less, respectively. A process for producing a polymer characterized by the above.   The method for producing a polymer according to any one of claims 1 to 6, wherein the megasonic frequency is 0.1 MHz to 100 MHz.   A polymer produced by using the polymer production method according to any one of claims 1 to 7 is used for at least a part of at least one of a substrate and an interlayer insulating film. Printed wiring board.   An electronic device in which a wiring layer is formed by using a polymer manufactured by the method for manufacturing a polymer according to any one of claims 1 to 7 as at least a part of an interlayer insulating film.   A transparent photosensitive polymer material characterized by consisting essentially of a polymer produced by using the method for producing a polymer according to any one of claims 1 to 7.   An optical fiber comprising substantially a polymer produced by using the method for producing a polymer according to any one of claims 1 to 7.   An optical device using a polymer produced by the method for producing a polymer according to any one of claims 1 to 7 as at least a part of an optical waveguide.   A polymer material for construction, characterized in that it substantially consists of a polymer produced by using the method for producing a polymer according to any one of claims 1 to 7.   A medical polymer material produced by using the method for producing a polymer according to any one of claims 1 to 7 and substantially consisting of a polymer.   A polymer material for food, comprising substantially a polymer produced by using the method for producing a polymer according to any one of claims 1 to 7.   An automobile, a ship, an airplane, a rocket, or a space vehicle substantially comprising a polymer produced by using the polymer production method according to any one of claims 1 to 7. Polymer member for use.   A semiconductor encapsulating material substantially comprising a polymer produced by using the method for producing a polymer according to any one of claims 1 to 7. A polymer material for covering an electric wire / wiring cable, substantially comprising a polymer produced by using the method for producing a polymer according to any one of claims 1 to 7.