Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
  • C08F4/32—Organic compounds
  • C08F4/34—Per-compounds with one peroxy-radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
  • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides

Definitions

• the present invention relates to a method for producing a copolymer, and specifically relates to a method for producing a copolymer having a large number of structural units derived from an aromatic vinyl compound and having a carboxy group and an epoxy group.
• Patterned films are used in the field of electronic materials such as liquid crystal display elements, and a photosensitive resin composition utilizing a photopolymerization reaction has been developed as one of resist materials used for forming this film.
• the photosensitive resin composition is required to be excellent in sensitivity and resolution (hereinafter also referred to as developability).
• developability the radiation-sensitive resin composition of Patent Document 1 has been developed.
• this radiation-sensitive resin composition contains a structural unit derived from (meth) acrylic acid having a carboxy group and a structural unit derived from glycidyl (meth) acrylate having an epoxy group, alkali development There is developability with a liquid, and resistance to the formed film is obtained. Furthermore, since this copolymer contains a structural unit derived from an aromatic vinyl compound, it is excellent in sensitivity and developability.
• the present invention has been made based on the above circumstances, and an object of the present invention is a method for producing a copolymer having a large number of structural units derived from an aromatic vinyl compound and having a carboxy group and an epoxy group.
• an object of the present invention to provide a method for producing a copolymer, which can carry out a polymerization reaction having a low residual monomer, a high conversion rate, and a copolymer having a low degree of dispersion.
• the present inventors have used a specific initiator in a method for producing a copolymer having a large number of structural units derived from an aromatic vinyl compound and having a carboxy group and an epoxy group.
• the inventors have found that the above problems can be solved by carrying out a polymerization reaction, and have completed the present invention.
• the content ratio of (A) aromatic vinyl compound is 30 to 80% by mass
• the content ratio of (B) glycidyl (meth) acrylate is 1 to 30% by mass
• Production of a copolymer having a step of polymerizing a monomer mixture having an acrylic acid content of 1 to 40% by mass in the presence of a dialkyl peroxydicarbonate represented by the formula (1) Is the method.
• Formula (1) R 1 —O (CO) OO (CO) O—R 2
• the component (D) used as an initiator in the production method of the present invention has a high addition capability, it is possible to accelerate the polymerization reaction of the aromatic vinyl compound (A) where unreacted monomers tend to remain. Become. Therefore, the residual monomer is reduced, the reaction efficiency can be improved, and a polymerization reaction having a high conversion rate can be performed. Further, since the polymerization temperature can be made relatively low, the reaction between the carboxy group and the epoxy group can be suppressed, and a copolymer having a low polydispersity can be obtained. Furthermore, since the component (D) is in a solution state at normal temperature and normal pressure, it is possible to use a dropping tank, and the handling amount is good, such as easy adjustment of the charging amount and continuous charging. That is, according to the production method of the present invention, a copolymer can be produced efficiently.
• the polymerization reaction is carried out with a low residual monomer and a high conversion rate.
• a copolymer having a low degree of dispersion can be obtained. Therefore, a photosensitive resin composition excellent in sensitivity and developability can be obtained by using the copolymer obtained by the production method of the present invention.
• light in the photosensitive resin composition includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.
• the method for producing a copolymer of the present invention includes at least (A) an aromatic vinyl compound, (B) glycidyl (meth) acrylate, and (C) (meth) acrylic acid, and further includes an optional component.
• a good monomer mixture is polymerized in the presence of a dialkyl peroxydicarbonate represented by the formula (1) (D) as an initiator.
• Formula (1) R 1 —O (CO) OO (CO) O—R 2
• the numerical range defined using the symbol “ ⁇ ” includes the numerical values at both ends (upper limit and lower limit) of “ ⁇ ”. For example, “2 to 5” represents 2 or more and 5 or less.
• the component (A) is an aromatic vinyl compound.
• the aromatic vinyl compound include styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene.
• the content ratio of the component (A) in the monomer mixture is 30 to 80% by mass.
• the content is preferably 40 to 75% by mass, and more preferably 45 to 70% by mass. If the amount is less than 30% by mass, the resolution may decrease when the copolymer is used in the photosensitive resin composition. On the other hand, when the amount is more than 80% by mass, the residual monomer increases, the conversion rate decreases, and the production efficiency may decrease.
• the component (B) is glycidyl (meth) acrylate, and examples thereof include glycidyl acrylate and glycidyl methacrylate, and glycidyl methacrylate is preferred because it is easily available industrially.
• glycidyl acrylate and glycidyl methacrylate can be used.
• the content ratio of the component (B) in the monomer mixture is 1 to 30% by mass, preferably 5 to 25% by mass.
• a component is (meth) acrylic acid and acrylic acid and methacrylic acid are mentioned. One or both of acrylic acid and methacrylic acid can be used.
• the content ratio of the component (C) in the monomer mixture is 1 to 40% by mass, preferably 5 to 30% by mass.
• Dialkyl peroxydicarbonate represented by formula (1)> (D) component which is an initiator used with the manufacturing method of this invention is the dialkyl peroxydicarbonate represented by Formula (1).
• Formula (1) R 1 —O (CO) OO (CO) O—R 2
• R 1 and R 2 include ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Heptyl group, n-octyl group, 2-ethylhexyl group and the like.
• dialkyl peroxydicarbonate represented by the formula (1) include, for example, diethyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, isopropyl-n-propyl peroxy Examples thereof include dicarbonate, normal butyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, t-butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and the like.
• di-n-propyl peroxydicarbonate, diethyl peroxydicarbonate, diisopropyl peroxydicarbonate, and isopropyl-n-propyl peroxydicarbonate are lower alkyl peroxydicarbonates, so they are relatively catalytically active. Is preferable from the viewpoint of high.
• the dialkyl peroxydicarbonate represented by the formula (1) is a low-temperature active dialkyl carbonate and has a relatively high catalytic activity.
• This initiator has a high addition capability and is active at low temperatures, so that the polymerization temperature can be made relatively low. Therefore, (A) the polymerization reaction of the aromatic vinyl compound is promoted, and a side reaction is suppressed to obtain a copolymer having a low polydispersity. Furthermore, since this initiator can be handled in a solution state at normal temperature and normal pressure, it can be continuously added using a dropping tank or the like. Therefore, since this initiator has good handleability, a copolymer can be produced efficiently.
• the usage-amount of a component can be suitably set according to the combination of the monomer to be used, reaction conditions, etc.
• the amount of the component (D) used is set to 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, particularly preferably 5 to 30 parts by weight with respect to 100 parts by weight of the total amount of the monomer mixture. be able to.
• the whole amount may be charged all at once, a part may be charged all at once and the rest may be dropped, or the whole amount may be dropped.
• it is preferable to add an initiator together with the monomer because the control of the reaction becomes easy, and an initiator may be added even after the monomer is dropped in order to reduce the residual monomer.
• the monomer mixture used in the production method of the present invention may contain one or more monomers other than the above components (A) to (C), and the content ratio thereof is simply It is 0 to 20% by mass in the monomer mixture.
• the other monomer is not particularly limited as long as it is a monomer other than the above components (A) to (C) and can be copolymerized. Acrylic ester monomers are preferred.
• ⁇ Polymerization reaction> When the monomer mixture is polymerized in the presence of the component (D) as an initiator, a method known as a method for performing normal radical polymerization can be employed, for example, solution polymerization, emulsion polymerization. Suspension polymerization or the like can be employed. For example, in solution polymerization, a method in which a solution containing a monomer and an initiator is dropped into a solvent or a solution containing a monomer to cause a polymerization reaction, or a solution containing a monomer and an initiator are contained.
• a method may be used in which a solution to be polymerized is dropped into a solution containing a solvent or a monomer to cause a polymerization reaction.
• the initiator may be used as a solid or may be used by mixing with a solvent.
• a chain transfer agent that is usually used may be used as necessary to adjust the molecular weight.
• the aging conditions are preferably a polymerization temperature and a polymerization time that can completely decompose the initiator.
• any solvent that can dissolve the monomer to be used can be used, and examples thereof include alcohols, ethers, ketones, amides, and esters. Can do. These solvents can be used alone, or can be used as a mixed solvent in which two or more kinds are mixed.
• the amount of the solvent is preferably, for example, 100 to 1,000 parts by mass with respect to 100 parts by mass of the total amount of the monomer mixture. When the amount of the solvent is within this range, the polymer solution can be easily stirred to be a uniform solution, and the molecular weight can be easily adjusted, so that the monomer hardly remains.
• the solution after the polymerization reaction may be used as it is for the preparation of the photosensitive resin composition, or may be commonly used for operations such as reprecipitation and solvent removal for the purpose of isolating the copolymer. After the polymer is isolated, it may be used for preparing a photosensitive resin composition.
• a polymerization reaction of a copolymer containing a large number of structural units derived from an aromatic vinyl compound and having a carboxy group and an epoxy group can be carried out at a high conversion rate, for example, a conversion rate of 80% or more.
• a copolymer having a low polydispersity for example, a copolymer having a polydispersity (Mw / Mn) of 3 or less can be obtained.
• the conversion rate of the copolymer can be determined by analyzing the amount of monomers contained in the polymer solution by gas chromatography (GC), and the polydispersity (Mw / Mn) of the copolymer is determined by gel permeation chromatography. It can be determined by graphic (GPC) measurement. Mw represents a weight average molecular weight, and Mn represents a number average molecular weight.
• a mass part represents the mass part with respect to 100 mass parts of total amounts of a monomer mixture
• mass% represents the content rate in a monomer mixture (total amount 100 mass%).
• the amount of monomer contained in the polymer solution was quantified by the following method, and the conversion was calculated.
• An analytical sample was prepared by dissolving 3 g of the polymer solution and 0.01 g of the internal standard substance biphenyl in 35 g of acetone. The sample was analyzed by a gas chromatograph (GC) under the following conditions and quantified by an internal standard method.
• GC device manufactured by Shimadzu Corporation, GC-2014 Detector: FID Injection temperature: 200 ° C Detector temperature: 250 ° C
• the monomer conversion rate was calculated from the material balance of the raw material and the amount of residual monomer.
• PGMEA Propylene glycol monomethyl ether acetate
• GMA Glycidyl methacrylate
• MAA Methacrylic acid
• EMA Ethyl methacrylate
• CHMA Cyclohexyl methacrylate
• NPP Di-n-propyl peroxydicarbonate (trade name: Parroyl NPP, manufactured by NOF Corporation) : 50% purity product)
• IPP Diisopropyl peroxydicarbonate (trade name: Parroyl IPP, NOF Corporation: 50% purity product)
• OPP Di-2-ethylhexyl peroxydicarbonate (trade name: Parroyl OPP, manufactured by NOF Corporation: 70% purity product)
• V-65 2,2′-azobis- (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
• MSD ⁇ -methylstyrene dimer (trade name: NOFMER MSD, manufactured by NOF Corporation) Pe
• Example 1 637 g (200 parts by mass) of PGMEA was introduced into a 2 liter separable flask equipped with a stirrer, a thermometer, a cooling tube, a dropping funnel, and a nitrogen introducing tube, and after raising the temperature to 65 ° C., 207.0 g (65 masses) of styrene. %), 63.7 g (20 mass%) of GMA, and 47.8 g (15 mass%) of MAA were added dropwise over 2 hours. In parallel, 89.2 g (14 parts by mass) of NPP was added dropwise over 2 hours. After completion of dropping, the mixture was aged for 2 hours to obtain a copolymer solution. The polymerization reaction was performed in a nitrogen atmosphere. When the obtained copolymer solution was evaluated, the conversion ratio was 85.8%. Moreover, Mw of the copolymer was 10,000 and Mw / Mn was 1.8.
• Example 2 Into a 2 liter separable flask equipped with a stirrer, thermometer, cooling tube, dropping funnel and nitrogen introducing tube, 654 g (200 parts by mass) of PGMEA was introduced, and after raising the temperature to 65 ° C., 212.4 g (65 masses) of styrene. %), 65.4 g (20 mass%) of GMA, and 49.0 g (15 mass%) of MAA were added dropwise over 2 hours. In parallel, 39.2 g (6 parts by mass) of NPP was added dropwise over 2 hours. After completion of dropping, the mixture was aged for 2 hours to obtain a copolymer solution. The polymerization reaction was performed in a nitrogen atmosphere. When the obtained copolymer solution was evaluated, the conversion rate was 80.2%. Moreover, Mw of the obtained copolymer was 51,000 and Mw / Mn was 2.6.
• Example 3 PGMEA 625 g (200 parts by mass) was introduced into a 2 liter separable flask equipped with a stirrer, thermometer, cooling tube, dropping funnel and nitrogen introduction tube, and after the temperature was raised to 65 ° C., 203.1 g of styrene (65 masses). %), 62.5 g (20 mass%) of GMA, and 46.9 g (15 mass%) of MAA were added dropwise over 2 hours. In parallel, 125 g (20 parts by mass) of NPP was added dropwise over 2 hours. After completion of dropping, the mixture was aged for 2 hours to obtain a copolymer solution. The polymerization reaction was performed in a nitrogen atmosphere. When the obtained copolymer solution was evaluated, the conversion rate was 87.6%. Moreover, Mw of the obtained copolymer was 5,400 and Mw / Mn was 1.7.
• Example 4 637 g (200 parts by mass) of PGMEA was introduced into a 2 liter separable flask equipped with a stirrer, a thermometer, a cooling tube, a dropping funnel and a nitrogen introducing tube, and after raising the temperature to 65 ° C., 207.0 g of styrene (65 Mass%), 63.7 g (20 mass%) of GMA, 31.8 g (10 mass%) of MAA, and 15.9 g (5 mass%) of EMA were added dropwise over 2 hours. In parallel, 89.2 g (14 parts by mass) of NPP was added dropwise over 2 hours. After completion of dropping, the mixture was aged for 2 hours to obtain a copolymer solution. The polymerization reaction was performed in a nitrogen atmosphere. When the obtained copolymer solution was evaluated, the conversion rate was 84.8%. Further, Mw of the obtained copolymer was 9,800, and Mw / Mn was 1.8.
• Example 5 637 g (200 parts by mass) of PGMEA was introduced into a 2 liter separable flask equipped with a stirrer, a thermometer, a cooling tube, a dropping funnel, and a nitrogen introducing tube, and after raising the temperature to 65 ° C., 207.0 g (65 masses) of styrene. %), 63.7 g (20 mass%) of GMA, 31.8 g (10 mass%) of MAA, and 15.9 g (5 mass%) of CHMA were added dropwise over 2 hours. In parallel, 89.2 g (14 parts by mass) of IPP was added dropwise over 2 hours. After completion of dropping, the mixture was aged for 2 hours to obtain a copolymer solution. The polymerization reaction was performed in a nitrogen atmosphere. When the obtained copolymer solution was evaluated, the conversion rate was 83.9%. Further, Mw of the obtained copolymer was 9,800, and Mw / Mn was 1.8.
• Example 6 637 g (200 parts by mass) of PGMEA and 6.4 g (2 parts by mass) of MSD were introduced into a 2 liter separable flask equipped with a stirrer, thermometer, cooling tube, dropping funnel and nitrogen introducing tube, and the temperature was raised to 65 ° C. Thereafter, 207.0 g (65 mass%) of styrene, 63.7 g (20 mass%) of GMA, 31.8 g (10 mass%) of MAA, and 15.9 g (5 mass%) of EMA were added dropwise over 2 hours. In parallel, 76.4 g (12 parts by mass) of NPP was added dropwise over 2 hours. After completion of dropping, the mixture was aged for 2 hours to obtain a copolymer solution. The polymerization reaction was performed in a nitrogen atmosphere. When the obtained copolymer solution was evaluated, the conversion rate was 87.8%. Further, Mw of the obtained copolymer was 8,800, and Mw / Mn was 1.8.
• Example 7 637 g (200 parts by mass) of PGMEA was introduced into a 2 liter separable flask equipped with a stirrer, a thermometer, a cooling tube, a dropping funnel, and a nitrogen introducing tube, and after raising the temperature to 65 ° C., 207.0 g (65 masses) of styrene. %), 63.7 g (20 mass%) of GMA, 31.8 g (10 mass%) of MAA, and 15.9 g (5 mass%) of CHMA were added dropwise over 2 hours. In parallel, 63.7 g (14 parts by mass) of OPP was added dropwise over 2 hours. After completion of dropping, the mixture was aged for 2 hours to obtain a copolymer solution.
• the polymerization reaction was performed in a nitrogen atmosphere.
• the conversion rate was 82.2%.
• Mw of the obtained copolymer was 9,600 and Mw / Mn was 2.4.
• Table 1 shows the results of evaluating the copolymer solutions and copolymers obtained in these examples.
• an initiator solution prepared by dissolving 22.7 g (7 parts by mass) of V-65 in 23 g (7 parts by mass) of PGMEA was added dropwise over 2 hours. After completion of dropping, the mixture was aged for 2 hours to obtain a copolymer solution. The polymerization reaction was performed in a nitrogen atmosphere. When the obtained copolymer solution was evaluated, the conversion rate was 65.4%. Further, Mw of the obtained copolymer was 11,000, and Mw / Mn was 2.6.
• an initiator solution prepared by dissolving 22.7 g (7 parts by mass) of V-65 in 20 g (6 parts by mass) of PGMEA was added dropwise over 2 hours.
• an initiator solution in which 3.2 g (1 part by mass) of V-65 was further dissolved in 3 g (1 part by mass) of PGMEA was added dropwise, and the copolymer was further aged for 2 hours.
• the polymerization reaction was performed in a nitrogen atmosphere. When the obtained copolymer solution was evaluated, the conversion was 77.8%. Further, Mw of the obtained copolymer was 25,000, and Mw / Mn was 3.6.
• the copolymer obtained by the production method of the present invention contains a large number of structural units derived from an aromatic vinyl compound and has a low polydispersity (Mw / Mm), so that it is used as a copolymer in a photosensitive resin composition.
• a photosensitive resin composition excellent in sensitivity and developability can be obtained.

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