WO2016080334A1 - Copolymer production method - Google Patents
Copolymer production method Download PDFInfo
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- WO2016080334A1 WO2016080334A1 PCT/JP2015/082080 JP2015082080W WO2016080334A1 WO 2016080334 A1 WO2016080334 A1 WO 2016080334A1 JP 2015082080 W JP2015082080 W JP 2015082080W WO 2016080334 A1 WO2016080334 A1 WO 2016080334A1
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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Abstract
Provided is a copolymer production method for producing a copolymer that includes many structural units derived from an aromatic vinyl compound, and has a carboxyl group and an epoxy group, whereby a polymerization reaction having a high conversion rate can be performed, with few residual monomers, and a copolymer having a low degree of dispersion can be obtained. This method copolymer production method involves a step in which a monomer mixture, which comprises (A) an aromatic vinyl compound contained in a ratio of 30 to 80 mass%, (B) a glycidyl (meth)acrylate contained in a ratio of 1 to 30 mass%, and (C) a (meth)acrylate contained in a ratio of 1 to 40 mass%, is polymerized in the presence of (D) a dialkyl peroxydicarbonate represented by formula (1). Formula (1): R1–OCOOOCOO–R2 [In formula (1), R1 and R2 each represent CnH2n+1 (n = 2 to 8), and R1 and R2 may be the same or different.]
Description
本発明は共重合体の製造方法に関し、詳細には、芳香族ビニル化合物由来の構造単位を多く含み、カルボキシ基およびエポキシ基を持つ共重合体を製造する方法に関する。
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.
液晶表示素子等の電子材料分野などではパターン形成された膜が使用され、この膜の形成に使用されるレジスト材料の一つとして、光重合反応を利用した感光性樹脂組成物が開発されている。感光性樹脂組成物は、感度および解像度（以下、現像性ともいう。）に優れることが求められており、例えば特許文献１の感放射線性樹脂組成物が開発されている。
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). For example, the radiation-sensitive resin composition of Patent Document 1 has been developed.
この感放射線性樹脂組成物に含まれる共重合体は、カルボキシ基を持つ（メタ）アクリル酸由来の構造単位とエポキシ基を持つ（メタ）アクリル酸グリシジル由来の構造単位とを含むので、アルカリ現像液による現像性があり、形成された膜に耐性が得られる。さらに、この共重合体は、芳香族ビニル化合物由来の構造単位を含むので、感度および現像性に優れている。
Since the copolymer contained in 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.
しかし、芳香族ビニル化合物を多く含む単量体混合物を共重合させる場合、従来の重合開始剤（以下、単に開始剤ともいう。）を使用して重合反応させると、通常の重合条件では残存単量体が多くなり転化率が低くなるという問題があった。残存単量体を減らすためには、通常、開始剤量を増加させたり、反応温度を上げたり、反応時間を長くしたりする手法が採られる。しかし、それらの場合、単量体中のカルボキシ基とエポキシ基による副反応が起こり易くなり、多分散度（Ｍｗ／Ｍｍ）の高い共重合体となるので、現像性が悪くなるという問題があった。
すなわち、従来の技術では、残存単量体が少なく、転化率の高い重合反応を行なうことは困難であり、また多分散度の低い共重合体が得られていなかった。 However, in the case of copolymerizing a monomer mixture containing a large amount of an aromatic vinyl compound, if a conventional polymerization initiator (hereinafter also simply referred to as an initiator) is used for the polymerization reaction, the remaining monomer can be obtained under normal polymerization conditions. There was a problem that the amount of the polymer increased and the conversion rate decreased. In order to reduce the residual monomer, generally, a method of increasing the amount of the initiator, raising the reaction temperature, or lengthening the reaction time is employed. However, in those cases, side reactions due to the carboxy group and the epoxy group in the monomer are likely to occur, resulting in a copolymer having a high polydispersity (Mw / Mm), resulting in poor developability. It was.
That is, according to the conventional technique, it is difficult to carry out a polymerization reaction having a low residual monomer and a high conversion rate, and a copolymer having a low polydispersity has not been obtained.
すなわち、従来の技術では、残存単量体が少なく、転化率の高い重合反応を行なうことは困難であり、また多分散度の低い共重合体が得られていなかった。 However, in the case of copolymerizing a monomer mixture containing a large amount of an aromatic vinyl compound, if a conventional polymerization initiator (hereinafter also simply referred to as an initiator) is used for the polymerization reaction, the remaining monomer can be obtained under normal polymerization conditions. There was a problem that the amount of the polymer increased and the conversion rate decreased. In order to reduce the residual monomer, generally, a method of increasing the amount of the initiator, raising the reaction temperature, or lengthening the reaction time is employed. However, in those cases, side reactions due to the carboxy group and the epoxy group in the monomer are likely to occur, resulting in a copolymer having a high polydispersity (Mw / Mm), resulting in poor developability. It was.
That is, according to the conventional technique, it is difficult to carry out a polymerization reaction having a low residual monomer and a high conversion rate, and a copolymer having a low polydispersity has not been obtained.
本発明は、以上のような事情に基づいてなされたものであり、その目的は、芳香族ビニル化合物由来の構造単位を多く含み、カルボキシ基およびエポキシ基を持つ共重合体を製造する方法であって、残存単量体が少なく、転化率の高い重合反応を行なうことができ、また分散度の低い共重合体が得られる、共重合体の製造方法を提供することである。
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. Thus, it is 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.
本発明者らは、上記課題に鑑み鋭意検討した結果、芳香族ビニル化合物由来の構造単位を多く含み、カルボキシ基およびエポキシ基を持つ共重合体を製造する方法において、特定の開始剤を用いて重合反応をさせることにより、上記課題を解決しうることを見出し、本発明を完成するに至った。
As a result of intensive studies in view of the above problems, 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.
すなわち本発明は、（Ａ）芳香族ビニル化合物の含有割合が３０～８０質量％であり、（Ｂ）（メタ）アクリル酸グリシジルの含有割合が１～３０質量％であり、（Ｃ）（メタ）アクリル酸の含有割合が１～４０質量％である単量体混合物を（Ｄ）式（１）で表されるジアルキルパーオキシジカーボネートの存在下で重合させる工程を有する、共重合体の製造方法である。
式（１） Ｒ１－Ｏ（ＣＯ）ＯＯ（ＣＯ）Ｏ－Ｒ２
〔式（１）中、Ｒ１およびＲ２はＣｎＨ２ｎ＋１（ｎ＝２～８）を示し、Ｒ１およびＲ２は同一でも良いし異なっていても良い。〕 That is, in 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, and (C) (meta ) 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
[In formula (1), R 1 and R 2 represent C n H 2n + 1 (n = 2 to 8), and R 1 and R 2 may be the same or different. ]
式（１） Ｒ１－Ｏ（ＣＯ）ＯＯ（ＣＯ）Ｏ－Ｒ２
〔式（１）中、Ｒ１およびＲ２はＣｎＨ２ｎ＋１（ｎ＝２～８）を示し、Ｒ１およびＲ２は同一でも良いし異なっていても良い。〕 That is, in 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, and (C) (meta ) 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
[In formula (1), R 1 and R 2 represent C n H 2n + 1 (n = 2 to 8), and R 1 and R 2 may be the same or different. ]
本発明の製造方法において開始剤として使用される（Ｄ）成分は、付加能力が高いので、未反応の単量体が残りやすい（Ａ）芳香族ビニル化合物の重合反応を促進させることが可能となる。したがって、残存単量体が少なくなり反応効率を向上させることが可能となり、転化率の高い重合反応を行なうことができる。
また重合温度を比較的低温にすることが可能であるので、カルボキシ基とエポキシ基との反応を抑制することができ、多分散度の低い共重合体を得ることができる。
さらに（Ｄ）成分は、常温・常圧下で溶液状態であるので滴下槽を使用することが可能であり、投入量の調整がし易く連続的に投入が可能であるなど取り扱い性が良い。すなわち、本発明の製造方法によれば、効率よく共重合体を製造することができる。 Since 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.
また重合温度を比較的低温にすることが可能であるので、カルボキシ基とエポキシ基との反応を抑制することができ、多分散度の低い共重合体を得ることができる。
さらに（Ｄ）成分は、常温・常圧下で溶液状態であるので滴下槽を使用することが可能であり、投入量の調整がし易く連続的に投入が可能であるなど取り扱い性が良い。すなわち、本発明の製造方法によれば、効率よく共重合体を製造することができる。 Since 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.
本発明によれば、芳香族ビニル化合物由来の構造単位を多く含み、カルボキシ基およびエポキシ基を持つ共重合体を製造する方法において、残存単量体が少なく、転化率の高い重合反応を行なうことができ、また分散度の低い共重合体を得ることができる。したがって、本発明の製造方法により得られた共重合体を用いることにより、感度および現像性に優れた感光性樹脂組成物を得ることができる。
なお、本明細書において感光性樹脂組成物における光は、可視光線、紫外線、遠紫外線、Ｘ線、荷電粒子線等を包含する。 According to the present invention, 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 polymerization reaction is carried out with a low residual monomer and a high conversion rate. In addition, 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.
In the present specification, light in the photosensitive resin composition includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.
なお、本明細書において感光性樹脂組成物における光は、可視光線、紫外線、遠紫外線、Ｘ線、荷電粒子線等を包含する。 According to the present invention, 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 polymerization reaction is carried out with a low residual monomer and a high conversion rate. In addition, 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.
In the present specification, light in the photosensitive resin composition includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.
以下、本発明の実施形態を説明する。
本発明の共重合体の製造方法は、（Ａ）芳香族ビニル化合物、（Ｂ）（メタ）アクリル酸グリシジル、および（Ｃ）（メタ）アクリル酸を少なくとも含み、さらに任意成分を含有しても良い単量体混合物を、開始剤である（Ｄ）式（１）で表されるジアルキルパーオキシジカーボネートの存在下で重合させる工程を有する。
式（１） Ｒ１－Ｏ（ＣＯ）ＯＯ（ＣＯ）Ｏ－Ｒ２
〔式（１）中、Ｒ１およびＲ２はＣｎＨ２ｎ＋１（ｎ＝２～８）を示し、Ｒ１およびＲ２は同一でも良いし異なっていても良い。〕 Embodiments of the present invention will be described below.
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
[In formula (1), R 1 and R 2 represent C n H 2n + 1 (n = 2 to 8), and R 1 and R 2 may be the same or different. ]
本発明の共重合体の製造方法は、（Ａ）芳香族ビニル化合物、（Ｂ）（メタ）アクリル酸グリシジル、および（Ｃ）（メタ）アクリル酸を少なくとも含み、さらに任意成分を含有しても良い単量体混合物を、開始剤である（Ｄ）式（１）で表されるジアルキルパーオキシジカーボネートの存在下で重合させる工程を有する。
式（１） Ｒ１－Ｏ（ＣＯ）ＯＯ（ＣＯ）Ｏ－Ｒ２
〔式（１）中、Ｒ１およびＲ２はＣｎＨ２ｎ＋１（ｎ＝２～８）を示し、Ｒ１およびＲ２は同一でも良いし異なっていても良い。〕 Embodiments of the present invention will be described below.
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
[In formula (1), R 1 and R 2 represent C n H 2n + 1 (n = 2 to 8), and R 1 and R 2 may be the same or different. ]
まず、上記（Ａ）～（Ｄ）の各成分について説明する。
なお、本明細書において記号「～」を用いて規定された数値範囲は「～」の両端（上限および下限）の数値を含むものとする。例えば「２～５」は２以上５以下を表す。 First, the components (A) to (D) will be described.
In the present specification, 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.
なお、本明細書において記号「～」を用いて規定された数値範囲は「～」の両端（上限および下限）の数値を含むものとする。例えば「２～５」は２以上５以下を表す。 First, the components (A) to (D) will be described.
In the present specification, 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.
＜（Ａ）芳香族ビニル化合物＞
（Ａ）成分は芳香族ビニル化合物であり、芳香族ビニル化合物としては、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ｍ－メチルスチレン、ｏ－メチルスチレン、ｐ－エチルスチレン、ｍ－エチルスチレン、ｏ－エチルスチレン、ｔ－ブチルスチレン、クロロスチレン、ヒドロキシスチレン、ｔ－ブトキシスチレン、ビニルトルエン、ビニルナフタレンなどが挙げられ、その中でもスチレン、α－メチルスチレン、ｐ－メチルスチレンおよびヒドロキシスチレンが好ましく、特にスチレンが好ましい。なお、（Ａ）成分として２種以上の芳香族ビニル化合物を用いてもよい。 <(A) Aromatic vinyl compound>
The component (A) is an aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene. , O-ethylstyrene, t-butylstyrene, chlorostyrene, hydroxystyrene, t-butoxystyrene, vinyltoluene, vinylnaphthalene, etc., among which styrene, α-methylstyrene, p-methylstyrene and hydroxystyrene are preferred. In particular, styrene is preferred. In addition, you may use 2 or more types of aromatic vinyl compounds as (A) component.
（Ａ）成分は芳香族ビニル化合物であり、芳香族ビニル化合物としては、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ｍ－メチルスチレン、ｏ－メチルスチレン、ｐ－エチルスチレン、ｍ－エチルスチレン、ｏ－エチルスチレン、ｔ－ブチルスチレン、クロロスチレン、ヒドロキシスチレン、ｔ－ブトキシスチレン、ビニルトルエン、ビニルナフタレンなどが挙げられ、その中でもスチレン、α－メチルスチレン、ｐ－メチルスチレンおよびヒドロキシスチレンが好ましく、特にスチレンが好ましい。なお、（Ａ）成分として２種以上の芳香族ビニル化合物を用いてもよい。 <(A) Aromatic vinyl compound>
The component (A) is an aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene. , O-ethylstyrene, t-butylstyrene, chlorostyrene, hydroxystyrene, t-butoxystyrene, vinyltoluene, vinylnaphthalene, etc., among which styrene, α-methylstyrene, p-methylstyrene and hydroxystyrene are preferred. In particular, styrene is preferred. In addition, you may use 2 or more types of aromatic vinyl compounds as (A) component.
単量体混合物中における（Ａ）成分の含有割合は、３０～８０質量％である。好ましくは４０～７５質量％であり、４５～７０質量％がより好ましい。３０質量％より少ない場合には、共重合体を感光性樹脂組成物に用いた際に解像度が低下するおそれがある。また８０質量％より多い場合には、残存単量体が多くなると共に転化率が下がり、製造効率が低下するおそれがある。
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.
＜（Ｂ）（メタ）アクリル酸グリシジル＞
（Ｂ）成分は（メタ）アクリル酸グリシジルであり、アクリル酸グリシジルおよびメタクリル酸グリシジルが挙げられ、工業的に容易に入手可能であることからメタアクリル酸グリシジルが好ましい。なお、アクリル酸グリシジルおよびメタクリル酸グリシジルのうち一方または両方を用いることができる。
単量体混合物中における（Ｂ）成分の含有割合は、１～３０質量％であり、好ましくは５～２５質量％である。 <(B) Glycidyl (meth) acrylate>
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. One or both of 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.
（Ｂ）成分は（メタ）アクリル酸グリシジルであり、アクリル酸グリシジルおよびメタクリル酸グリシジルが挙げられ、工業的に容易に入手可能であることからメタアクリル酸グリシジルが好ましい。なお、アクリル酸グリシジルおよびメタクリル酸グリシジルのうち一方または両方を用いることができる。
単量体混合物中における（Ｂ）成分の含有割合は、１～３０質量％であり、好ましくは５～２５質量％である。 <(B) Glycidyl (meth) acrylate>
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. One or both of 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.
＜（Ｃ）（メタ）アクリル酸＞
（Ｃ）成分は（メタ）アクリル酸であり、アクリル酸およびメタクリル酸が挙げられる。なお、アクリル酸およびメタクリル酸のうち一方または両方を用いることができる。
単量体混合物中における（Ｃ）成分の含有割合は、１～４０質量％であり、好ましくは５～３０質量％である。 <(C) (Meth) acrylic acid>
(C) 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.
（Ｃ）成分は（メタ）アクリル酸であり、アクリル酸およびメタクリル酸が挙げられる。なお、アクリル酸およびメタクリル酸のうち一方または両方を用いることができる。
単量体混合物中における（Ｃ）成分の含有割合は、１～４０質量％であり、好ましくは５～３０質量％である。 <(C) (Meth) acrylic acid>
(C) 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.
＜（Ｄ）式（１）で表されるジアルキルパーオキシジカルボネート＞
本発明の製造方法で用いられる開始剤である（Ｄ）成分は、式（１）で表されるジアルキルパーオキシジカルボネートである。
式（１） Ｒ１－Ｏ（ＣＯ）ＯＯ（ＣＯ）Ｏ－Ｒ２
式（１）中、Ｒ１およびＲ２はＣｎＨ２ｎ＋１（ｎ＝２～８）を示し、Ｒ１およびＲ２は同一でも良いし異なっていても良い。Ｒ１およびＲ２としては、具体的には、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基などが挙げられる。 <(D) 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
In Formula (1), R 1 and R 2 represent C n H 2n + 1 (n = 2 to 8), and R 1 and R 2 may be the same or different. Specific examples of 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.
本発明の製造方法で用いられる開始剤である（Ｄ）成分は、式（１）で表されるジアルキルパーオキシジカルボネートである。
式（１） Ｒ１－Ｏ（ＣＯ）ＯＯ（ＣＯ）Ｏ－Ｒ２
式（１）中、Ｒ１およびＲ２はＣｎＨ２ｎ＋１（ｎ＝２～８）を示し、Ｒ１およびＲ２は同一でも良いし異なっていても良い。Ｒ１およびＲ２としては、具体的には、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基などが挙げられる。 <(D) 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
In Formula (1), R 1 and R 2 represent C n H 2n + 1 (n = 2 to 8), and R 1 and R 2 may be the same or different. Specific examples of 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.
式（１）で表されるジアルキルパーオキシジカルボネートの具体例としては、例えば、ジエチルパーオキシジカーボネート、ジ－ｎ－プロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、イソプロピル－ｎ－プロピルパーオキシジカーボネート、ノルマルブチルパーオキシジカーボネート、ジ－ｓｅｃ－ブチルパーオキシジカーボネート、ｔ－ブチルパーオキシジカーボネート、ジ－２－エチルヘキシルパーオキシジカーボネートなどが挙げられる。その中でもジ－ｎ－プロピルパーオキシジカーボネート、ジエチルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、イソプロピル－ｎ－プロピルパーオキシジカーボネートが、低級アルキルのパーオキシジカーボネートであるので、比較的触媒活性が高い点で好ましい。
Specific examples of the 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. Among them, 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.
式（１）で表されるジアルキルパーオキシジカルボネートは、低温活性のジアルキルカーボネートであり、触媒活性が比較的高い。この開始剤は、付加能力が高く、低温活性であるので重合温度を比較的低温にすることが可能である。そのため、（Ａ）芳香族ビニル化合物の重合反応を促進させ、また副反応を抑えて多分散度の低い共重合体が得られる。さらに、この開始剤は、常温・常圧下で溶液状態にて取り扱いが可能なため、滴下槽などを使用して連続的に投入することが可能である。したがって、この開始剤は取り扱い性が良好であるため、効率よく共重合体を製造することができる。
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.
（Ｄ）成分の使用量は、用いる単量体の組み合わせや、反応条件などに応じて適宜設定することができる。例えば、単量体混合物の総量１００質量部に対して、（Ｄ）成分の使用量を０．１～１００質量部、好ましくは１～５０質量部、特に好ましくは５～３０質量部に設定することができる。
なお、開始剤の投入に際しては、全量を一括仕込みしてもよいし、一部を一括仕込みして残りを滴下してもよく、あるいは全量を滴下してもよい。また、単量体とともに開始剤を添加すると、反応の制御が容易となるので好ましく、さらに残存単量体を低減するために単量体滴下後にも開始剤を添加してもよい。 (D) The usage-amount of a component can be suitably set according to the combination of the monomer to be used, reaction conditions, etc. For example, 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.
In addition, when charging the initiator, 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. Moreover, 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.
なお、開始剤の投入に際しては、全量を一括仕込みしてもよいし、一部を一括仕込みして残りを滴下してもよく、あるいは全量を滴下してもよい。また、単量体とともに開始剤を添加すると、反応の制御が容易となるので好ましく、さらに残存単量体を低減するために単量体滴下後にも開始剤を添加してもよい。 (D) The usage-amount of a component can be suitably set according to the combination of the monomer to be used, reaction conditions, etc. For example, 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.
In addition, when charging the initiator, 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. Moreover, 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.
＜その他の単量体＞
本発明の製造方法で用いられる単量体混合物には、上記（Ａ）～（Ｃ）成分以外の他の単量体を１種または２種以上含んでいてもよく、その含有割合は、単量体混合物中において０～２０質量％である。
他の単量体としては、上記（Ａ）～（Ｃ）成分以外の単量体であり、かつ共重合が可能である単量体であれば特に限定されるものではないが、（メタ）アクリル酸エステル系単量体が好ましい。例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸－２－エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸－２－メトキシエチル、（メタ）アクリル酸－３－メトキシブチル、（メタ）アクリル酸－２－ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸のエチレンオキサイド付加物などを挙げることができる。なお、（メタ）アクリル酸は、アクリル酸およびメタクリル酸を表す。 <Other monomers>
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. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate , Heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acryl Acid phenyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate , Hydroxybutyl (meth) acrylate, stearyl (meth) acrylate, (me ) Acrylate, dicyclopentanyl and the like of ethylene oxide adduct of (meth) acrylic acid. In addition, (meth) acrylic acid represents acrylic acid and methacrylic acid.
本発明の製造方法で用いられる単量体混合物には、上記（Ａ）～（Ｃ）成分以外の他の単量体を１種または２種以上含んでいてもよく、その含有割合は、単量体混合物中において０～２０質量％である。
他の単量体としては、上記（Ａ）～（Ｃ）成分以外の単量体であり、かつ共重合が可能である単量体であれば特に限定されるものではないが、（メタ）アクリル酸エステル系単量体が好ましい。例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸－２－エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸－２－メトキシエチル、（メタ）アクリル酸－３－メトキシブチル、（メタ）アクリル酸－２－ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸のエチレンオキサイド付加物などを挙げることができる。なお、（メタ）アクリル酸は、アクリル酸およびメタクリル酸を表す。 <Other monomers>
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. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate , Heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acryl Acid phenyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate , Hydroxybutyl (meth) acrylate, stearyl (meth) acrylate, (me ) Acrylate, dicyclopentanyl and the like of ethylene oxide adduct of (meth) acrylic acid. In addition, (meth) acrylic acid represents acrylic acid and methacrylic acid.
＜重合反応＞
上記単量体混合物を開始剤である（Ｄ）成分の存在下で重合させるに際しては、通常のラジカル重合を行う方法として知られている方法を採用することができ、例えば、溶液重合、乳化重合、懸濁重合などを採用することができる。例えば、溶液重合においては、単量体および開始剤を含有する溶液を、溶媒または単量体を含有する溶液に滴下して重合反応させる方法や、単量体を含有する溶液と開始剤を含有する溶液を各々別に、溶媒または単量体を含有する溶液に滴下して重合反応させる方法などを挙げることができる。また開始剤は固体のまま使用しても、溶媒と混合して使用しても良い。
重合反応時には、分子量調整のために、必要に応じて、通常用いられる連鎖移動剤を用いてもよい。 <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. For example, 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.
In the polymerization reaction, a chain transfer agent that is usually used may be used as necessary to adjust the molecular weight.
上記単量体混合物を開始剤である（Ｄ）成分の存在下で重合させるに際しては、通常のラジカル重合を行う方法として知られている方法を採用することができ、例えば、溶液重合、乳化重合、懸濁重合などを採用することができる。例えば、溶液重合においては、単量体および開始剤を含有する溶液を、溶媒または単量体を含有する溶液に滴下して重合反応させる方法や、単量体を含有する溶液と開始剤を含有する溶液を各々別に、溶媒または単量体を含有する溶液に滴下して重合反応させる方法などを挙げることができる。また開始剤は固体のまま使用しても、溶媒と混合して使用しても良い。
重合反応時には、分子量調整のために、必要に応じて、通常用いられる連鎖移動剤を用いてもよい。 <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. For example, 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.
In the polymerization reaction, a chain transfer agent that is usually used may be used as necessary to adjust the molecular weight.
重合反応時には、単量体混合物、開始剤、必要に応じて連鎖移動剤の投入後、熟成を行うことが好ましい。熟成条件としては、開始剤を完全に分解することのできる重合温度、重合時間とするのが好ましい。
In the polymerization reaction, it is preferable to perform aging after adding a monomer mixture, an initiator, and, if necessary, a chain transfer agent. The aging conditions are preferably a polymerization temperature and a polymerization time that can completely decompose the initiator.
溶液重合による重合反応に用いられる溶媒としては、使用する単量体を溶解可能な溶剤であれば使用することができ、例えば、アルコール類、エーテル類、ケトン類、アミド類、エステル類を挙げることができる。これらの溶媒は、単独で使用することができ、また２種以上を混合した混合溶媒として使用することができる。
溶媒量としては、単量体混合物の総量１００質量部に対して、例えば、１００～１，０００質量部が好ましい。溶媒量がこの範囲のとき、重合体溶液が撹拌しやすく均一な溶液にできるとともに、分子量の調整も行いやすく、単量体が残存しにくい。 As the solvent used in the polymerization reaction by solution polymerization, 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.
溶媒量としては、単量体混合物の総量１００質量部に対して、例えば、１００～１，０００質量部が好ましい。溶媒量がこの範囲のとき、重合体溶液が撹拌しやすく均一な溶液にできるとともに、分子量の調整も行いやすく、単量体が残存しにくい。 As the solvent used in the polymerization reaction by solution polymerization, 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.
重合反応後の溶液は、そのまま感光性樹脂組成物の調製に使用しても良いし、共重合体を単離するために通常行なわれる操作、例えば再沈殿、溶剤除去などの操作を行って共重合体を単離した後、感光性樹脂組成物の調製に使用しても良い。
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.
本発明の製造方法によれば、芳香族ビニル化合物由来の構造単位を多く含み、カルボキシ基およびエポキシ基を持つ共重合体の重合反応を高い転化率、例えば転化率８０％以上で行なうことができる。
また、本発明の製造方法により、多分散度の低い共重合体、例えば、多分散度（Ｍｗ／Ｍｎ）が３以下の共重合体を得ることができる。
なお、共重合体の転化率は重合体溶液に含まれる単量体量をガスクロマトグラフ（ＧＣ）により分析して求めることができ、共重合体の多分散度（Ｍｗ／Ｍｎ）はゲル浸透クロマトグラフィー（ＧＰＣ）測定により求めることができる。Ｍｗは重量平均分子量を、Ｍｎは数平均分子量をそれぞれ表す。 According to the production method of the present invention, 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. .
Further, by the production method of the present invention, 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.
また、本発明の製造方法により、多分散度の低い共重合体、例えば、多分散度（Ｍｗ／Ｍｎ）が３以下の共重合体を得ることができる。
なお、共重合体の転化率は重合体溶液に含まれる単量体量をガスクロマトグラフ（ＧＣ）により分析して求めることができ、共重合体の多分散度（Ｍｗ／Ｍｎ）はゲル浸透クロマトグラフィー（ＧＰＣ）測定により求めることができる。Ｍｗは重量平均分子量を、Ｍｎは数平均分子量をそれぞれ表す。 According to the production method of the present invention, 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. .
Further, by the production method of the present invention, 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.
以下、実施例および比較例を挙げて本発明をさらに詳細に説明する。なお、各種物性値、測定、および評価は以下の方法に従った。また、実施例および比較例において、質量部は単量体混合物の総量１００質量部に対する質量部を表し、質量％は単量体混合物（総量１００質量％）中における含有割合を表す。
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. Various physical property values, measurements, and evaluations were performed according to the following methods. Moreover, in an Example and a comparative example, a mass part represents the mass part with respect to 100 mass parts of total amounts of a monomer mixture, and mass% represents the content rate in a monomer mixture (total amount 100 mass%).
（１）転化率
重合体溶液に含まれる単量体量を下記方法により定量し、転化率を算出した。
重合体溶液３ｇと内部標準物質のビフェニル０．０１ｇをアセトン３５ｇに溶解させ、分析試料を調製した。試料をガスクロマトグラフ（ＧＣ）により下記条件で分析し、内部標準法により定量した。
ＧＣ装置：（株）島津製作所製、ＧＣ－２０１４
検出器：ＦＩＤ
インジェクション温度：２００℃
検出器温度：２５０℃
カラム温度：５０℃１０分保持、毎分１０℃昇温、２５０℃１０分保持
カラム：アジレント・テクノロジー（株）製、ＤＢ－１７（内径０．２５ｍｍ、長さ３０ｍ、膜厚０．２５μｍ）
そして、原料の物質収支および残存単量体量から単量体の転化率（％）を算出した。 (1) Conversion 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
Column temperature: held at 50 ° C. for 10 minutes, heated at 10 ° C. per minute, held at 250 ° C. for 10 minutes Column: manufactured by Agilent Technologies, DB-17 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)
The monomer conversion rate (%) was calculated from the material balance of the raw material and the amount of residual monomer.
重合体溶液に含まれる単量体量を下記方法により定量し、転化率を算出した。
重合体溶液３ｇと内部標準物質のビフェニル０．０１ｇをアセトン３５ｇに溶解させ、分析試料を調製した。試料をガスクロマトグラフ（ＧＣ）により下記条件で分析し、内部標準法により定量した。
ＧＣ装置：（株）島津製作所製、ＧＣ－２０１４
検出器：ＦＩＤ
インジェクション温度：２００℃
検出器温度：２５０℃
カラム温度：５０℃１０分保持、毎分１０℃昇温、２５０℃１０分保持
カラム：アジレント・テクノロジー（株）製、ＤＢ－１７（内径０．２５ｍｍ、長さ３０ｍ、膜厚０．２５μｍ）
そして、原料の物質収支および残存単量体量から単量体の転化率（％）を算出した。 (1) Conversion 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
Column temperature: held at 50 ° C. for 10 minutes, heated at 10 ° C. per minute, held at 250 ° C. for 10 minutes Column: manufactured by Agilent Technologies, DB-17 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)
The monomer conversion rate (%) was calculated from the material balance of the raw material and the amount of residual monomer.
（２）重合体の重量平均分子量（Ｍｗ）、多分散度（Ｍｗ／Ｍｎ）
ゲル浸透クロマトグラフィー（ＧＰＣ）測定により、下記条件で求めた。
ＧＰＣ装置：東ソー（株）製、ＨＬＣ－８２２０
カラム：昭和電工（株）製、Ｓｈｏｄｅｘ ＫＦ－８０５Ｌ
溶媒：テトラヒドロフラン
標準物質：ポリスチレン (2) Weight average molecular weight (Mw) of polymer, polydispersity (Mw / Mn)
It calculated | required on the following conditions by the gel permeation chromatography (GPC) measurement.
GPC device: manufactured by Tosoh Corporation, HLC-8220
Column: Showex Denko, Shodex KF-805L
Solvent: Tetrahydrofuran Standard: Polystyrene
ゲル浸透クロマトグラフィー（ＧＰＣ）測定により、下記条件で求めた。
ＧＰＣ装置：東ソー（株）製、ＨＬＣ－８２２０
カラム：昭和電工（株）製、Ｓｈｏｄｅｘ ＫＦ－８０５Ｌ
溶媒：テトラヒドロフラン
標準物質：ポリスチレン (2) Weight average molecular weight (Mw) of polymer, polydispersity (Mw / Mn)
It calculated | required on the following conditions by the gel permeation chromatography (GPC) measurement.
GPC device: manufactured by Tosoh Corporation, HLC-8220
Column: Showex Denko, Shodex KF-805L
Solvent: Tetrahydrofuran Standard: Polystyrene
また実施例中の略号は以下のとおりである。
ＰＧＭＥＡ：酢酸プロピレングリコールモノメチルエーテル
ＧＭＡ：メタクリル酸グリシジル
ＭＡＡ：メタクリル酸
ＥＭＡ：メタクリル酸エチル
ＣＨＭＡ：メタクリル酸シクロヘキシル
ＮＰＰ：ジ－ｎ－プロピルパーオキシジカルボネート（商品名：パーロイルＮＰＰ、日油（株）製：純度５０％品）
ＩＰＰ：ジイソプロピルパーオキシジカルボネート（商品名：パーロイルＩＰＰ、日油（株）製：純度５０％品）
ＯＰＰ：ジ－２－エチルヘキシルパーオキシジカルボネート（商品名：パーロイルＯＰＰ、日油（株）製：純度７０％品）
Ｖ－６５：２，２’－アゾビス－（２，４－ジメチルバレロニトリル）（和光純薬工業（株）製）
ＭＳＤ：α－メチルスチレンダイマー（商品名：ノフマーＭＳＤ、日油（株）製）
パーオクタＮＤ：１，１，３，３－テトラメチルブチル－パーオキシネオデカネート（日油（株）製：純度７０％品） Abbreviations in the examples are as follows.
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: α-methylstyrene dimer (trade name: NOFMER MSD, manufactured by NOF Corporation)
Perocta ND: 1,1,3,3-tetramethylbutyl-peroxyneodecanate (manufactured by NOF Corporation: 70% purity product)
ＰＧＭＥＡ：酢酸プロピレングリコールモノメチルエーテル
ＧＭＡ：メタクリル酸グリシジル
ＭＡＡ：メタクリル酸
ＥＭＡ：メタクリル酸エチル
ＣＨＭＡ：メタクリル酸シクロヘキシル
ＮＰＰ：ジ－ｎ－プロピルパーオキシジカルボネート（商品名：パーロイルＮＰＰ、日油（株）製：純度５０％品）
ＩＰＰ：ジイソプロピルパーオキシジカルボネート（商品名：パーロイルＩＰＰ、日油（株）製：純度５０％品）
ＯＰＰ：ジ－２－エチルヘキシルパーオキシジカルボネート（商品名：パーロイルＯＰＰ、日油（株）製：純度７０％品）
Ｖ－６５：２，２’－アゾビス－（２，４－ジメチルバレロニトリル）（和光純薬工業（株）製）
ＭＳＤ：α－メチルスチレンダイマー（商品名：ノフマーＭＳＤ、日油（株）製）
パーオクタＮＤ：１，１，３，３－テトラメチルブチル－パーオキシネオデカネート（日油（株）製：純度７０％品） Abbreviations in the examples are as follows.
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: α-methylstyrene dimer (trade name: NOFMER MSD, manufactured by NOF Corporation)
Perocta ND: 1,1,3,3-tetramethylbutyl-peroxyneodecanate (manufactured by NOF Corporation: 70% purity product)
（実施例１）
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ４７．８ｇ（１５質量％）を２時間かけて滴下した。並行して、ＮＰＰ８９．２ｇ（１４質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８５．８％であった。また共重合体のＭｗは１０，０００であり、Ｍｗ／Ｍｎは１．８であった。 (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.
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ４７．８ｇ（１５質量％）を２時間かけて滴下した。並行して、ＮＰＰ８９．２ｇ（１４質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８５．８％であった。また共重合体のＭｗは１０，０００であり、Ｍｗ／Ｍｎは１．８であった。 (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.
（実施例２）
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６５４ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２１２．４ｇ（６５質量％）、ＧＭＡ６５．４ｇ（２０質量％）、ＭＡＡ４９．０ｇ（１５質量％）を２時間かけて滴下した。並行して、ＮＰＰ３９．２ｇ（６質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８０．２％であった。また得られた共重合体のＭｗは５１，０００であり、Ｍｗ／Ｍｎは２．６であった。 (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.
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６５４ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２１２．４ｇ（６５質量％）、ＧＭＡ６５．４ｇ（２０質量％）、ＭＡＡ４９．０ｇ（１５質量％）を２時間かけて滴下した。並行して、ＮＰＰ３９．２ｇ（６質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８０．２％であった。また得られた共重合体のＭｗは５１，０００であり、Ｍｗ／Ｍｎは２．６であった。 (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.
（実施例３）
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６２５ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２０３．１ｇ（６５質量％）、ＧＭＡ６２．５ｇ（２０質量％）、ＭＡＡ４６．９ｇ（１５質量％）を２時間かけて滴下した。並行して、ＮＰＰ１２５ｇ（２０質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８７．６％であった。また得られた共重合体のＭｗは５，４００であり、Ｍｗ／Ｍｎは１．７であった。 (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.
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６２５ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２０３．１ｇ（６５質量％）、ＧＭＡ６２．５ｇ（２０質量％）、ＭＡＡ４６．９ｇ（１５質量％）を２時間かけて滴下した。並行して、ＮＰＰ１２５ｇ（２０質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８７．６％であった。また得られた共重合体のＭｗは５，４００であり、Ｍｗ／Ｍｎは１．７であった。 (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.
（実施例４）
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部％）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ３１．８ｇ（１０質量％）、ＥＭＡ１５．９ｇ（５質量％）を２時間かけて滴下した。並行して、ＮＰＰ８９．２ｇ（１４質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８４．８％であった。また得られた共重合体のＭｗは９，８００であり、Ｍｗ／Ｍｎは１．８であった。 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.
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部％）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ３１．８ｇ（１０質量％）、ＥＭＡ１５．９ｇ（５質量％）を２時間かけて滴下した。並行して、ＮＰＰ８９．２ｇ（１４質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８４．８％であった。また得られた共重合体のＭｗは９，８００であり、Ｍｗ／Ｍｎは１．８であった。 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.
（実施例５）
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ３１．８ｇ（１０質量％）、ＣＨＭＡ１５．９ｇ（５質量％）を２時間かけて滴下した。並行して、ＩＰＰ８９．２ｇ（１４質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８３．９％であった。また得られた共重合体のＭｗは９，８００であり、Ｍｗ／Ｍｎは１．８であった。 (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.
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ３１．８ｇ（１０質量％）、ＣＨＭＡ１５．９ｇ（５質量％）を２時間かけて滴下した。並行して、ＩＰＰ８９．２ｇ（１４質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８３．９％であった。また得られた共重合体のＭｗは９，８００であり、Ｍｗ／Ｍｎは１．８であった。 (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.
（実施例６）
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部）、ＭＳＤ６．４ｇ（２質量部）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ３１．８ｇ（１０質量％）、ＥＭＡ１５．９ｇ（５質量％）を２時間かけて滴下した。並行して、ＮＰＰ７６．４ｇ（１２質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８７．８％であった。また得られた共重合体のＭｗは８，８００であり、Ｍｗ／Ｍｎは１．８であった。 (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.
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部）、ＭＳＤ６．４ｇ（２質量部）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ３１．８ｇ（１０質量％）、ＥＭＡ１５．９ｇ（５質量％）を２時間かけて滴下した。並行して、ＮＰＰ７６．４ｇ（１２質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８７．８％であった。また得られた共重合体のＭｗは８，８００であり、Ｍｗ／Ｍｎは１．８であった。 (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.
（実施例７）
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ３１．８ｇ（１０質量％）、ＣＨＭＡ１５．９ｇ（５質量％）を２時間かけて滴下した。並行して、ＯＰＰ６３．７ｇ（１４質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８２．２％であった。また得られた共重合体のＭｗは９，６００であり、Ｍｗ／Ｍｎは２．４であった。
これら実施例で得られた共重合体溶液および共重合体を評価した結果を表１に示す。 (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.
When the obtained copolymer solution was evaluated, the conversion rate was 82.2%. Moreover, 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.
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ３１．８ｇ（１０質量％）、ＣＨＭＡ１５．９ｇ（５質量％）を２時間かけて滴下した。並行して、ＯＰＰ６３．７ｇ（１４質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は８２．２％であった。また得られた共重合体のＭｗは９，６００であり、Ｍｗ／Ｍｎは２．４であった。
これら実施例で得られた共重合体溶液および共重合体を評価した結果を表１に示す。 (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.
When the obtained copolymer solution was evaluated, the conversion rate was 82.2%. Moreover, 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.
（比較例１）
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６２６ｇ（１９３質量部）、ＭＳＤ３．２ｇ（１質量部）を導入し、７０℃に昇温後、スチレン２１１．０ｇ（６５質量％）、ＧＭＡ３２．５ｇ（１０質量％）、ＭＡＡ４８．７ｇ（１５質量％）、ＥＭＡ３２．５ｇ（１０質量％）を２時間かけて滴下した。並行して、Ｖ－６５の２２．７ｇ（７質量部）をＰＧＭＥＡ２３ｇ（７質量部）に溶解した開始剤溶液を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は６５．４％であった。また得られた共重合体のＭｗは１１，０００であり、Ｍｗ／Ｍｎは２．６であった。 (Comparative Example 1)
626 g (193 parts by mass) of PGMEA and 3.2 g (1 part by mass) of MSD were 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 the temperature was raised to 70 ° C. Then, 211.0 g (65 mass%) of styrene, 32.5 g (10 mass%) of GMA, 48.7 g (15 mass%) of MAA, and 32.5 g (10 mass%) of EMA were added dropwise over 2 hours. In parallel, 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.
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６２６ｇ（１９３質量部）、ＭＳＤ３．２ｇ（１質量部）を導入し、７０℃に昇温後、スチレン２１１．０ｇ（６５質量％）、ＧＭＡ３２．５ｇ（１０質量％）、ＭＡＡ４８．７ｇ（１５質量％）、ＥＭＡ３２．５ｇ（１０質量％）を２時間かけて滴下した。並行して、Ｖ－６５の２２．７ｇ（７質量部）をＰＧＭＥＡ２３ｇ（７質量部）に溶解した開始剤溶液を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は６５．４％であった。また得られた共重合体のＭｗは１１，０００であり、Ｍｗ／Ｍｎは２．６であった。 (Comparative Example 1)
626 g (193 parts by mass) of PGMEA and 3.2 g (1 part by mass) of MSD were 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 the temperature was raised to 70 ° C. Then, 211.0 g (65 mass%) of styrene, 32.5 g (10 mass%) of GMA, 48.7 g (15 mass%) of MAA, and 32.5 g (10 mass%) of EMA were added dropwise over 2 hours. In parallel, 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.
（比較例２）
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６２４ｇ（１９３質量部）、ＭＳＤ３．２ｇ（１質量部）を導入し、７０℃に昇温後、スチレン２１０．４ｇ（６５質量％）、ＧＭＡ３２．４ｇ（１０質量％）、ＭＡＡ４８．５ｇ（１５質量％）、ＥＭＡ３２．４ｇ（１０質量％）を２時間かけて滴下した。並行して、Ｖ－６５の２２．７ｇ（７質量部）をＰＧＭＥＡ２０ｇ（６質量部）に溶解した開始剤溶液を２時間かけて滴下した。終了後４時間熟成した後、さらに追加的にＶ－６５の３．２ｇ（１質量部）をＰＧＭＥＡ３ｇ（１質量部）に溶解した開始剤溶液を滴下し、さらに２時間熟成して共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は７７．８％であった。また得られた共重合体のＭｗは２５，０００であり、Ｍｗ／Ｍｎは３．６であった。 (Comparative Example 2)
624 g (193 parts by mass) of PGMEA and 3.2 g (1 part by mass) of MSD were 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 the temperature was raised to 70 ° C. Then, 210.4 g (65 mass%) of styrene, 32.4 g (10 mass%) of GMA, 48.5 g (15 mass%) of MAA, and 32.4 g (10 mass%) of EMA were added dropwise over 2 hours. In parallel, 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. After aging for 4 hours after completion, 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. A solution was obtained. 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.
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６２４ｇ（１９３質量部）、ＭＳＤ３．２ｇ（１質量部）を導入し、７０℃に昇温後、スチレン２１０．４ｇ（６５質量％）、ＧＭＡ３２．４ｇ（１０質量％）、ＭＡＡ４８．５ｇ（１５質量％）、ＥＭＡ３２．４ｇ（１０質量％）を２時間かけて滴下した。並行して、Ｖ－６５の２２．７ｇ（７質量部）をＰＧＭＥＡ２０ｇ（６質量部）に溶解した開始剤溶液を２時間かけて滴下した。終了後４時間熟成した後、さらに追加的にＶ－６５の３．２ｇ（１質量部）をＰＧＭＥＡ３ｇ（１質量部）に溶解した開始剤溶液を滴下し、さらに２時間熟成して共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は７７．８％であった。また得られた共重合体のＭｗは２５，０００であり、Ｍｗ／Ｍｎは３．６であった。 (Comparative Example 2)
624 g (193 parts by mass) of PGMEA and 3.2 g (1 part by mass) of MSD were 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 the temperature was raised to 70 ° C. Then, 210.4 g (65 mass%) of styrene, 32.4 g (10 mass%) of GMA, 48.5 g (15 mass%) of MAA, and 32.4 g (10 mass%) of EMA were added dropwise over 2 hours. In parallel, 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. After aging for 4 hours after completion, 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. A solution was obtained. 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.
（比較例３）
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ４７．８ｇ（１５質量％）を２時間かけて滴下した。並行して、パーオクタＮＤ６３．７ｇ（１４質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は７０．８％であった。また得られた共重合体のＭｗは９，０００であり、Ｍｗ／Ｍｎは１．９であった。
これら比較例で得られた共重合体溶液および共重合体を評価した結果を表２に示す。 (Comparative Example 3)
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, 63.7 g (14 parts by mass) of perocta ND 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 70.8%. Moreover, Mw of the obtained copolymer was 9,000 and Mw / Mn was 1.9.
Table 2 shows the results of evaluating the copolymer solutions and copolymers obtained in these comparative examples.
攪拌器、温度計、冷却管、滴下ロートおよび窒素導入管を備えた２リットルのセパラブルフラスコに、ＰＧＭＥＡ６３７ｇ（２００質量部）を導入し、６５℃に昇温後、スチレン２０７．０ｇ（６５質量％）、ＧＭＡ６３．７ｇ（２０質量％）、ＭＡＡ４７．８ｇ（１５質量％）を２時間かけて滴下した。並行して、パーオクタＮＤ６３．７ｇ（１４質量部）を２時間かけて滴下した。滴下終了後２時間熟成させ、共重合体溶液を得た。重合反応は窒素雰囲気下で行なった。
得られた共重合体溶液を評価したところ、転化率は７０．８％であった。また得られた共重合体のＭｗは９，０００であり、Ｍｗ／Ｍｎは１．９であった。
これら比較例で得られた共重合体溶液および共重合体を評価した結果を表２に示す。 (Comparative Example 3)
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, 63.7 g (14 parts by mass) of perocta ND 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 70.8%. Moreover, Mw of the obtained copolymer was 9,000 and Mw / Mn was 1.9.
Table 2 shows the results of evaluating the copolymer solutions and copolymers obtained in these comparative examples.
表１に示される結果から、本発明の製造法に係る実施例によれば、残存単量体量が少なく、転化率が高い重合反応が行われており、多分散度の低い共重合体が効率よく得られていることが分かる。
From the results shown in Table 1, according to the examples of the production method of the present invention, a polymerization reaction with a low residual monomer amount and a high conversion rate is performed, and a copolymer with low polydispersity is obtained. It turns out that it is obtained efficiently.
一方、表２に示される結果から、本発明で用いられる開始剤以外の開始剤を用いた比較例１および３では、残存単量体が多く、重合反応の転化率が低くなることが分かる。また、開始剤を追加して二段階で重合反応を行なった場合（比較例２）、転化率は向上するものの、多分散度の高い共重合体が得られることが分かる。
On the other hand, the results shown in Table 2 show that in Comparative Examples 1 and 3 using an initiator other than the initiator used in the present invention, the amount of residual monomer is large and the conversion rate of the polymerization reaction is low. In addition, when the polymerization reaction is performed in two stages by adding an initiator (Comparative Example 2), it can be seen that a copolymer having a high polydispersity can be obtained although the conversion rate is improved.
本発明の製造方法により得られる共重合体は、芳香族ビニル化合物由来の構造単位を多く含み、また多分散度（Ｍｗ／Ｍｍ）が低いので、感光性樹脂組成物における共重合体として用いることにより、感度および現像性に優れた感光性樹脂組成物を得ることができる。
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. Thus, a photosensitive resin composition excellent in sensitivity and developability can be obtained.
Claims (1)
- （Ａ）芳香族ビニル化合物の含有割合が３０～８０質量％であり、（Ｂ）（メタ）アクリル酸グリシジルの含有割合が１～３０質量％であり、（Ｃ）（メタ）アクリル酸の含有割合が１～４０質量％である単量体混合物を（Ｄ）式（１）で表されるジアルキルパーオキシジカーボネートの存在下で重合させる工程を有する、共重合体の製造方法。
式（１） Ｒ１－Ｏ（ＣＯ）ＯＯ（ＣＯ）Ｏ－Ｒ２
〔式（１）中、Ｒ１およびＲ２はＣｎＨ２ｎ＋１（ｎ＝２～８）を示し、Ｒ１およびＲ２は同一でも良いし異なっていても良い。〕 (A) The content of aromatic vinyl compound is 30 to 80% by mass, (B) the content of glycidyl (meth) acrylate is 1 to 30% by mass, and (C) the content of (meth) acrylic acid A method for producing a copolymer, comprising a step of polymerizing a monomer mixture having a ratio of 1 to 40% by mass in the presence of a dialkyl peroxydicarbonate represented by formula (1) (D).
Formula (1) R 1 —O (CO) OO (CO) O—R 2
[In formula (1), R 1 and R 2 represent C n H 2n + 1 (n = 2 to 8), and R 1 and R 2 may be the same or different. ]
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| JP2007538109A (en) * | 2003-06-27 | 2007-12-27 | アクゾ ノーベル ナムローゼ フェンノートシャップ | (Co) Polymerization method for producing polymer |
| JP2012063626A (en) * | 2010-09-16 | 2012-03-29 | Jsr Corp | Radiation-sensitive resin composition, interlayer insulating film, formation method of interlayer insulating film, and display element |
| CN103838083A (en) * | 2012-11-20 | 2014-06-04 | 奇美实业股份有限公司 | Photosensitive resin composition, color filter formed by same and liquid crystal display element |
| JP2015199820A (en) * | 2014-04-08 | 2015-11-12 | 日油株式会社 | Method for manufacturing glycidyl methacrylate polymer |
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| CN101440146A (en) | 2007-11-23 | 2009-05-27 | 佛山市顺德区汉达精密电子科技有限公司 | Compatibilizer |
| CN103772621A (en) | 2014-01-09 | 2014-05-07 | 抚顺市久丰合成树脂制造有限公司 | Water-soluble acrylic alkyd resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS50101481A (en) * | 1974-01-10 | 1975-08-12 | ||
| JPH03126784A (en) * | 1989-10-11 | 1991-05-29 | Japan Synthetic Rubber Co Ltd | Composition for tacky adhesive agent |
| JP2007538109A (en) * | 2003-06-27 | 2007-12-27 | アクゾ ノーベル ナムローゼ フェンノートシャップ | (Co) Polymerization method for producing polymer |
| JP2012063626A (en) * | 2010-09-16 | 2012-03-29 | Jsr Corp | Radiation-sensitive resin composition, interlayer insulating film, formation method of interlayer insulating film, and display element |
| CN103838083A (en) * | 2012-11-20 | 2014-06-04 | 奇美实业股份有限公司 | Photosensitive resin composition, color filter formed by same and liquid crystal display element |
| JP2015199820A (en) * | 2014-04-08 | 2015-11-12 | 日油株式会社 | Method for manufacturing glycidyl methacrylate polymer |
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| JPWO2016080334A1 (en) | 2017-09-28 |
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