CN108699169B - Method for producing resin - Google Patents
Method for producing resin Download PDFInfo
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- CN108699169B CN108699169B CN201780012718.4A CN201780012718A CN108699169B CN 108699169 B CN108699169 B CN 108699169B CN 201780012718 A CN201780012718 A CN 201780012718A CN 108699169 B CN108699169 B CN 108699169B
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- polymerization initiator
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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
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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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention aims to provide a method for producing a resin using radical polymerization, which can obtain sufficient reproducibility of molecular weight and has a small amount of residual monomers. In order to achieve the above object, the present invention provides a method for producing a resin, comprising: adding a radical polymerizable monomer and a thermal radical polymerization initiator to a reaction vessel to polymerize the radical polymerizable monomer at a temperature 20 to 70 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator.
Description
Technical Field
The present invention relates to a method for producing a resin obtained by radical polymerization. More specifically, the present invention relates to a method for producing a resin at a specific temperature when polymerizing a radical polymerizable monomer using a thermal radical polymerization initiator.
Background
In recent years, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in the fields of various coatings, printing, paints, adhesives, and the like from the viewpoints of resource saving and energy saving. In the field of electronic materials such as printed wiring boards, photosensitive resin compositions curable with active energy rays are also used for resists (resists) such as solder resists, color filters (color filters), black matrices (black matrices), photo spacers (photo spacers), and protective films.
The use of resins obtained by radical polymerization is known in the above-mentioned fields, and various methods for producing resins obtained by general radical polymerization have been proposed (patent documents 1 and 2). However, conventional methods for producing resins by radical polymerization have problems such as insufficient reproducibility of molecular weight (reproducibility), insufficient mass productivity (mass productivity), and a large amount of residual monomers.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2002-265390
Patent document 2: japanese patent laid-open No. 2008-266555
Disclosure of Invention
Problems to be solved by the invention
As described above, conventional methods for producing resins by radical polymerization sometimes do not have reproducibility of molecular weight, have a large amount of residual monomers, and are difficult to industrially mass-produce.
Accordingly, the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a method for producing a resin using radical polymerization, which can obtain sufficient reproducibility of a molecular weight and has a small amount of residual monomers.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found the following facts, thereby completing the present invention: the above problem can be solved by setting the temperature to be 20 to 70 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator when the radical polymerizable monomer is polymerized using the thermal radical polymerization initiator.
Namely, the present invention provides:
(1) a method of making a resin, comprising: a step 1 of adding a radical polymerizable monomer and a thermal radical polymerization initiator to a reaction vessel and polymerizing the radical polymerizable monomer at a temperature 20 to 70 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator;
(2) the method for producing a resin according to (1), wherein the radical polymerizable monomer and the thermal radical polymerization initiator are added dropwise into a reaction vessel;
(3) the method for producing a resin according to (1) or (2), wherein a radical polymerizable monomer and a thermal radical polymerization initiator are added after the temperature in the reaction vessel is set to be 20 to 70 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator;
(4) the method for producing a resin according to any one of (1) to (3), comprising: a step 2 of reacting the radical polymerizable monomer for 0.5 to 3 hours after the addition of the radical polymerizable monomer is completed;
(5) the method for producing a resin according to any one of (1) to (4), wherein the thermal radical polymerization initiator is a peroxide;
(6) the method for producing a resin according to any one of (1) to (5), wherein the thermal radical polymerization initiator has a 10-hour half-life temperature of 60 to 110 ℃;
(7) the method for producing a resin according to any one of (1) to (6), wherein the addition time of the radical polymerizable monomer is 60 to 300 minutes;
(8) the method for producing a resin according to any one of (1) to (7), comprising: a step 3 of, after completion of the step 1 or the step 2, further setting the temperature in the reaction vessel to a temperature which is not lower than a temperature which is 20 ℃ lower than the 10-hour half-life temperature of the thermal radical polymerization initiator but lower than a temperature which is 20 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator to perform polymerization;
(9) the method for producing a resin according to (8), wherein in the step 3, the polymerization time is 60 to 300 minutes;
(10) the method for producing a resin according to (8) or (9), wherein in the step 3, an additional thermal radical polymerization initiator is added;
(11) the method for producing a resin according to any one of (8) to (10), wherein in the step 3, an additional radical polymerizable monomer is added;
(12) the method for producing a resin according to any one of (1) to (11), wherein the radical polymerizable monomer contains (meth) acrylic acid;
(13) the method for producing a resin according to (12), wherein an unsaturated group is introduced by adding glycidyl (meth) acrylate to a carboxyl group derived from (meth) acrylic acid of the resin;
(14) the method for producing a resin according to (12), wherein the acid value of the resin is 10 to 300 KOHmg/g; and
(15) the method for producing a resin according to any one of (1) to (14), wherein the weight average molecular weight of the resin in terms of polystyrene is 1000 to 50000.
Effects of the invention
The production method of the present invention can provide a resin having sufficient reproducibility of molecular weight and a small amount of residual monomer. Therefore, the production method of the present invention can be used for industrial mass production of resins because of good reproducibility. Moreover, the manufacturing method of the present invention has the following advantages: since the residual monomer content is small, the residual monomer is less volatilized when heated in a coating material or the like using a resin, and contamination of a production apparatus or the like can be suppressed.
Detailed Description
The present invention will be described in detail below.
The polymerization of the radically polymerizable monomer of the present invention can be carried out in a batch operation in a reaction vessel.
The reaction vessel used in the present invention is not particularly limited as long as it is a reaction vessel industrially used for polymerizing a radical polymerizable monomer. For example, there may be mentioned: a reaction vessel having a mixing function and a temperature adjusting function, and having a supply port and an extraction port through which a raw material can be supplied and a reaction liquid can be extracted.
As the thermal radical polymerization initiator used in the present invention, a thermal radical polymerization initiator which generates thermal radicals by heat is generally used, and any of an organic peroxide-based initiator and an azo-based initiator can be used. As the organic peroxide-based initiator, for example, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxycarbonate, peroxydicarbonate and the like are preferable, and among them, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester is preferable, and peroxyester is particularly preferable. As the azo initiator, for example, 2 ' -azobisisobutyronitrile, 2 ' -azobis (2-methylbutyronitrile), methyl 2, 2 ' -azobisisobutyrate, and the like are preferable. These may be used alone or in combination of two or more.
The temperature of the thermal radical polymerization initiator used in the present invention is preferably 60 to 110 ℃ in a 10-hour half-life period, and more preferably 70 to 100 ℃.
The 10-hour half-life temperature is a temperature at which the time (half-life) until the concentration of the thermal radical polymerization initiator is reduced to half of the initial value when the thermal radical polymerization initiator is dissolved in the solvent is 10 hours. The 10-hour half-life can be calculated by a known method or a method described in a known document. When a commercially available product is used, the values described in the catalog and the specification may be used.
The amount of the thermal radical polymerization initiator used is not particularly limited, but is generally 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, when the total charge amount of the polymerizable monomer is 100 parts by mass.
< working procedure 1 >
In the present invention, a radical polymerizable monomer and a thermal radical polymerization initiator are added to a reaction vessel, and the radical polymerizable monomer is subjected to a polymerization reaction in the reaction vessel.
The polymerization reaction may be carried out in the presence or absence of a solvent according to a radical polymerization method well known in the art. For example, the radical polymerizable monomer may be dissolved in a solvent if necessary, and then polymerized together with a thermal radical polymerization initiator at a temperature 20 to 70 ℃ higher than the 10-hour half-life temperature of the polymerization initiator.
The method of adding the radical polymerizable monomer and the thermal radical polymerization initiator to the reaction vessel is not particularly limited, and it is preferable to add them to the reaction vessel by dropwise addition in view of easy control of the amount to be added, the rate of addition, the time of addition, and the like. Further, they may be mixed and added as a mixture, or may be added separately.
When the radical polymerizable monomer and the thermal radical polymerization initiator are added to the reaction vessel, either one or both of them may be dissolved in a solvent. In this case, the mixed solvent is added to the reaction vessel in an amount of 0 to 100 parts by mass, preferably 0 to 50 parts by mass, based on 100 parts by mass of the radically polymerizable monomer. The mixed solvent is added to the reaction vessel in an amount of 100 to 10000 parts by mass, preferably 150 to 5000 parts by mass, based on 100 parts by mass of the thermal radical polymerization initiator. When a mixture obtained by mixing a radical polymerizable monomer and a thermal radical polymerization initiator is added to a reaction vessel, the solvent is added to the reaction vessel in an amount of 0 to 100 parts by mass, preferably 0 to 50 parts by mass, based on 100 parts by mass of the mixture.
The time for adding the radically polymerizable monomer is not particularly limited, but it is usually 30 minutes to 300 minutes, preferably 60 minutes to 250 minutes, to the reaction vessel. In addition, the time for adding the thermal radical polymerization initiator to the reaction vessel is not particularly limited, but the thermal radical polymerization initiator is usually added in 30 minutes to 300 minutes, preferably 60 minutes to 250 minutes. In view of the efficiency of the operation, the time for adding the radical polymerizable monomer and the thermal radical polymerization initiator may be adjusted to be the same.
In addition, when the mixture of the radical polymerizable monomer and the thermal radical polymerization initiator is added to the reaction vessel, the time for the addition is not limited, but the addition is usually carried out for 30 minutes to 300 minutes, preferably for 60 minutes to 250 minutes.
When the radical polymerizable monomer and the thermal radical polymerization initiator are dissolved in the solvent and added to the reaction vessel by dropping, the dropping rate is not particularly limited, but when the total amount of the radical polymerizable monomer and the solvent is set to 100ml, the dropping rate of the radical polymerizable monomer is usually 0.1 ml/min to 5 ml/min, preferably 0.2 ml/min to 4 ml/min. When the total amount of the thermal radical polymerization initiator and the solvent is set to 100ml, the dropping rate of the thermal radical polymerization initiator is usually 0.1 ml/min to 5 ml/min, and preferably 0.2 ml/min to 4 ml/min. The dropping rate at which the radical polymerizable monomer and the thermal radical polymerization initiator are dissolved in the solvent as a mixture and added to the reaction vessel is usually 0.1 ml/min to 5 ml/min, preferably 0.2 ml/min to 4 ml/min, assuming that the total amount of the radical polymerizable monomer, the thermal radical polymerization initiator and the solvent is 100 ml.
In the polymerization reaction, the temperature in the reaction vessel is set to a temperature 20 to 70 ℃ higher, preferably 30 to 60 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator used. When the reaction is carried out in this temperature range, the amount of residual monomers can be sufficiently reduced, and the reproducibility of resin production is also excellent. In the polymerization reaction, the temperature may vary within this temperature range, but from the viewpoint of the operation efficiency, it is preferable to carry out the reaction at a constant temperature. When two or more thermal radical polymerization initiators are used, the polymerization reaction is carried out at a temperature 20 to 70 ℃ higher than the 10-hour half-life temperature of all the thermal radical polymerization initiators.
In addition, from the viewpoint of efficiently carrying out the polymerization reaction, it is preferable that the temperature in the reaction vessel is adjusted to a temperature 20 to 70 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator before adding the radical polymerizable monomer and/or the thermal radical polymerization initiator.
< step 2 >
After the addition of the radical polymerizable monomer and the thermal radical polymerization initiator to the reaction vessel is completed, the polymerization reaction is carried out at a temperature 20 to 70 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator. The time for the polymerization reaction is not particularly limited, but is usually 30 minutes to 300 minutes, preferably 30 minutes to 180 minutes. The polymerization reaction herein is preferably carried out while stirring.
< step 3 >
After the polymerization reaction is carried out at a temperature 20 to 70 ℃ higher than the 10-hour half-life temperature, an additional polymerization reaction may be carried out at a temperature which is 20 ℃ lower than the 10-hour half-life temperature and lower than the temperature 20 ℃ higher than the 10-hour half-life temperature. Further, the amount of residual monomer can be further reduced by carrying out the polymerization reaction.
In step 3, a thermal radical polymerization initiator and a radical polymerizable monomer may be further added. The kind of the thermal radical polymerization initiator to be added at the additional polymerization reaction may be the same as or different from that at the polymerization reaction in step 1.
When the thermal radical polymerization initiators added in step 1 and step 3 are different, the polymerization reaction is carried out in a range of not less than 20 ℃ lower than the 10-hour half-life temperature of all the thermal radical polymerization initiators and less than 20 ℃ higher than the 10-hour half-life temperature of all the thermal radical polymerization initiators.
In this case, the thermal radical polymerization initiator may be optionally dissolved in a solvent and added dropwise or the like to the reaction vessel. From the viewpoint of shortening the production time of the resin and improving the production efficiency, it is desirable to charge the thermal radical polymerization initiator added at the time of the additional polymerization reaction into the reaction vessel at one time.
In the step 3, the amount used is not particularly limited when a thermal radical polymerization initiator is further added, but is generally 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, when the total charge amount of the polymerizable monomers is 100 parts by mass.
In step 3, when a radical polymerizable monomer is further added, the radical polymerizable monomer may be the same as or different from the radical polymerizable monomer used in the first polymerization reaction. In addition, two or more kinds of radical polymerizable monomers may be used.
In this case, the radical polymerizable monomer may be optionally dissolved in a solvent and added dropwise or in one portion to the reaction vessel. From the viewpoint of shortening the production time of the resin and improving the production efficiency, it is desirable to charge the radical polymerizable monomer added in step 3 into the reaction vessel at once.
The reaction time in the step 3 is not particularly limited, but is usually 60 to 300 minutes, preferably 120 to 240 minutes. When the thermal radical polymerization initiator and/or the radical polymerizable monomer is added dropwise to the reaction vessel, the reaction is usually carried out for 60 to 300 minutes, preferably 120 to 240 minutes, after completion of the addition. After completion of the step 3, the treatment is preferably carried out at a temperature 20 to 70 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator for 30 to 600 minutes.
The radical polymerizable monomer used in the polymerization reaction of the present invention is not particularly limited, and examples thereof include: norbornene, dicyclopentadiene, or aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetamidostyrene; conjugated diene compounds such as butadiene, isoprene and chloroprene; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, rosin (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1, 1, 1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoroisopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (, 3- (N, N-dimethylamino) propyl (meth) acrylate, triphenylmethyl (meth) acrylate, phenyl (meth) acrylate, cumyl (meth) acrylate, 4-phenoxyphenyl (meth) acrylate, diphenoxyethyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, N-pentyl methacrylate, isoamyl acrylate, N-hexyl methacrylate, 2-ethylhexyl acrylate, N-octyl methacrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, methoxy-triethylene glycol acrylate, ethoxy-diethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate (trade name: AM-90G, methyl ethyl methacrylate, ethyl propyl methacrylate, butyl methacrylate, manufactured by shinkamura chemical industries), 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycerol mono (meth) acrylate, phenoxyethyl acrylate, phenoxy-polyethylene glycol acrylate (trade name: LIGHT ACRYLATE P-200A, manufactured by Kyoeisha chemical Co., Ltd.), o-phenoxybenzyl acrylate, M-phenoxybenzyl acrylate, p-phenoxybenzyl acrylate, the reaction product of (meth) acryloyloxyethyl isocyanate (i.e., 2-isocyanatoethyl (meth) acrylate) and caprolactam, the reaction product of (meth) acryloyloxyethyl isocyanate and propylene glycol monomethyl ether, α -bromo (meth) acrylic acid, β -furyl (meth) acrylate, glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate and lactone adducts thereof (for example, CYCLOMER A200, M100, 3, 4-epoxycyclohexylmethyl-3', (meth) acrylate compounds such as mono (meth) acrylate of 4' -epoxycyclohexanecarboxylate, epoxide of dicyclopentenyl (meth) acrylate, epoxide of dicyclopentenyloxyethyl (meth) acrylate, and the like; carboxyl group-containing ethylenically unsaturated compounds such as (meth) acrylic acid, itaconic acid, crotonic acid, cinnamic acid, and maleic acid, and substitutes thereof; (meth) acrylamides such as (meth) acrylamide, N-dimethylamide (meth) acrylate, N-diethylamide (meth) acrylate, N-dipropylamide (meth) acrylate, N-diisopropylamide (meth) acrylate, and anthracylamide (meth) acrylate; vinyl compounds such as (meth) acryloylaniline, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene; unsaturated dicarboxylic acid diester compounds such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; and the like. These radically polymerizable monomers may be used alone or in combination of two or more. Among them, from the viewpoint of applying the resin to various resists, it is preferable to use an ethylenically unsaturated compound containing at least a carboxyl group, and it is more preferable to use (meth) acrylic acid.
The solvent usable in the polymerization reaction is not particularly limited, and examples thereof include: (poly) alkylene glycol monoalkyl ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly) alkylene glycol monoalkyl ether acetate compounds such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl butyrate, ester compounds such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbon compounds such as toluene and xylene; carboxylic acid amide compounds such as N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide; and the like. These solvents may be used alone or in combination of two or more.
Among them, preferred are (poly) alkylene glycol ether solvents such as (poly) alkylene glycol monoalkyl ether compounds and (poly) alkylene glycol monoalkyl ether acetate compounds, and more preferred are propylene glycol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
The total amount of the solvent used in the polymerization reaction of the present invention is not particularly limited, but is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, when the total amount of the charged radical polymerizable monomers is 100 parts by mass. In particular, by setting the amount of the solvent to 1000 parts by mass or less, the decrease in molecular weight of the polymer due to chain transfer can be suppressed, and the viscosity of the polymer can be controlled within an appropriate range. Further, by setting the amount of the solvent to 30 parts by mass or more, abnormal polymerization reaction can be prevented to stably progress the polymerization reaction, and coloring and gelation of the polymer can also be prevented.
When the product of the present invention is applied to various resist materials, it is preferable that the side chain has an acid group or a polymerizable unsaturated bond. The acid group can be introduced by using an ethylenically unsaturated compound containing at least a carboxyl group as a radical polymerizable monomer. The modified polycarbonate can also be obtained by the modification method (I) described below. The polymerizable unsaturated bond can be obtained by, for example, carrying out the modification reaction of the following (II).
(I) The modification method of (2):
an epoxy group-containing ethylenically unsaturated compound such as glycidyl (meth) acrylate is used as a radical polymerizable monomer. Epoxy groups contained in the molecules of a resin obtained by radical polymerization are cleaved with a polymerizable unsaturated monobasic acid such as (meth) acrylic acid, and the hydroxyl groups generated by the cleavage are reacted with a polybasic acid or an anhydride thereof.
In the case of using the modification method of the above-mentioned (I), the reaction of the resin obtained by the method of the present invention with the adduct can be carried out according to a conventional method. The modification reaction may be carried out without removing the solvent after the completion of the polymerization reaction, and for example, the modification reaction may be carried out by adding a polymerizable unsaturated monobasic acid to the reaction solvent containing the resin, further adding a polymerization inhibitor and a catalyst, reacting at 50 to 150 ℃, preferably 80 to 130 ℃, further adding a polybasic acid or an anhydride thereof, and reacting at 50 to 150 ℃, preferably 80 to 130 ℃. Examples of the polybasic acid or anhydride thereof include: tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, succinic anhydride, and the like.
(II) modification method:
an ethylenically unsaturated compound containing at least a carboxyl group is used as a radical polymerizable monomer. The carboxyl group contained in the molecule of the resin obtained by radical polymerization is reacted with a (meth) acrylate monomer having a functional group reactive with the carboxyl group, such as an epoxy group or a hydroxyl group.
In the case of the modification method of (II), as in the case of the modification method of (I), the modification reaction may be carried out without removing the solvent after the completion of the polymerization reaction in the production method of the present invention, and the reaction may be carried out at 50 to 150 ℃, preferably 80 to 130 ℃, by adding a (meth) acrylate monomer having a functional group reactive with a carboxyl group and a catalyst to the reaction solvent containing the resin obtained by the method of the present invention, and adding a polymerization inhibitor as necessary to prevent gelation.
When the resin obtained by the production method of the present invention has an acid group, the acid value (JIS K69015.3) can be selected as appropriate, but when the resin is used as a photosensitive polymer, the acid value is usually 10 to 300KOHmg/g, preferably 20 to 200 KOHmg/g.
The weight average molecular weight of the resin obtained by the present invention can be adjusted depending on the application, but when used in various resist materials, it is preferably 1000 to 50000, more preferably 3000 to 40000, from the viewpoint of improvement in thermal yellowing resistance and development property.
The weight average molecular weight in the present invention is a weight average molecular weight in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC) under the following conditions.
A chromatographic column: SHODEX (registered trademark) LF-804+ LF-804 (manufactured by SHOWA ELECTRIC CORPORATION)
Temperature of the column: 40 deg.C
Sample preparation: 0.2% by mass tetrahydrofuran solution of copolymer
Developing solvent: tetrahydrofuran (THF)
A detector: differential refractometer (SHODEX (registered trademark) RI-71S) (manufactured by Showa Denko K.K.)
Flow rate: 1mL/min
The photosensitive resin composition containing a polymerizable resin obtained from the resin produced in the present invention is suitably used as various resists, particularly for producing resists incorporated in color filters, black matrices, optical spacers, protective films, and overcoats (overcoatates) of organic EL displays, liquid crystal display devices, and solid-state image pickup elements.
Examples
The present invention will be described in detail below with reference to examples and comparative examples.
The amounts of residual monomers in the following examples and comparative examples were measured by GPC under the conditions described above in the same manner as the weight average molecular weight.
The reproducibility of the weight average molecular weight was determined according to the following criteria.
Criterion for reproducibility
O: the same polymerization reaction was repeated twice, and the rate of change in the second weight average molecular weight ((second weight average molecular weight-first weight average molecular weight)/first weight average molecular weight. times.100) was within. + -. 10%
X: the same polymerization was repeated twice, and the rate of change in the weight average molecular weight of the second time deviated from the range of. + -. 10%
< example 1 >
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 128.8g of propylene glycol monomethyl ether acetate was charged, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 ℃.
Subsequently, a radical polymerizable monomer composed of 38.7g of methacrylic acid, 22.0g of tricyclodecyl methacrylate and 79.2g of benzyl methacrylate and a mixture of 79.3g of propylene glycol monomethyl ether acetate and 2.0g of tert-butyl 2-ethylhexanoate peroxide (thermal radical polymerization initiator, manufactured by Nichigan Co., Ltd., PERBUTYL (registered trademark) O: 10-hour half-life temperature 72 ℃) were added dropwise to the flask from a dropping funnel over 2 hours, respectively. After the completion of the dropwise addition, the mixture was further stirred at 120 ℃ for 2 hours to conduct polymerization reaction, thereby obtaining a carboxyl group-containing resin solution having a weight-average molecular weight of 17500 and a solid acid value of 180 KOHmg/g.
The total amount of the residual monomers was measured, and the result was 0.8 mass%. Further, the same reaction was repeated, and as a result, the weight average molecular weight was 18000 and the reproducibility of the molecular weight was good.
< example 2 >
The reaction was carried out in the same manner as above except that the thermal radical polymerization initiator was changed to 1, 1, 3, 3-tetramethylbutyl peroxy-2-ethylhexanoate (PEROCTA (registered trademark) O: 10-hour half-life temperature 65 ℃ C., manufactured by Nichigan Co., Ltd.) and the reaction temperature was set to 109 ℃ to obtain a carboxyl group-containing resin solution having a weight-average molecular weight of 18500 and a solid acid value of 180 KOHmg/g. The total amount of the residual monomers was measured, and the result was 0.7% by mass. Further, the same reaction was repeated, and as a result, the weight average molecular weight was 19300 and the reproducibility of the molecular weight was good.
< example 3 >
The reaction was carried out in the same manner as except that the thermal radical polymerization initiator was changed to t-butyl peroxybenzoate (Kayabutyl B (registered trademark): 10-hour half-life temperature 105 ℃ C., manufactured by Nippon chemical Co., Ltd.) and the reaction temperature was 127 ℃ to obtain a carboxyl group-containing resin solution having a weight-average molecular weight of 14800 and a solid acid value of 180 KOHmg/g. The total amount of the residual monomers was measured, and the result was 0.6 mass%. Further, the same reaction was repeated, and as a result, the weight average molecular weight was 15100 and the reproducibility of the molecular weight was good.
< example 4 >
Propylene glycol monomethyl ether acetate (2.8 g) and tert-butyl 2-ethylhexanoate peroxide (0.7 g) (thermal radical polymerization initiator, manufactured by Nichigan Ltd., PERBUTYL (registered trademark) O: 10-hour half-life temperature 72 ℃ C.) were added to the solution of example 1, and the mixture was put into a flask and reacted at 90 ℃ for 3 hours (step 3) to obtain a carboxyl group-containing resin solution having a weight-average molecular weight of 17300 and a solid acid value of 180 KOHmg/g.
< example 5 >
The reaction was carried out in the same manner as in example 1 except that 37.0g of methacrylic acid was used, to obtain a carboxyl group-containing resin solution having a weight-average molecular weight of 17300 and a solid acid value of 180 KOHmg/g.
Further, 2.8g of propylene glycol monomethyl ether acetate and 0.7g of t-butyl peroxy-2-ethylhexanoate (thermal radical polymerization initiator, manufactured by Nichigan Co., Ltd., PERBUTYL (registered trademark) O: 10-hour half-life temperature 72 ℃ C.) and 1.7g of methacrylic acid were added, and the mixture was put into a flask and reacted at 90 ℃ for 3 hours to obtain a carboxyl group-containing resin solution having a weight average molecular weight of 17100 and a solid acid value of 180 KOHmg/g.
< example 6 >
21.3g of glycidyl methacrylate, 0.5g of hydroquinone as a polymerization inhibitor and 0.5g of triphenylphosphine as a catalyst were put into the solution of example 4, and the mixture was heated at 110 ℃ for 10 hours while blowing low-oxygen air into which nitrogen gas was injected so that the oxygen concentration was 4 to 6 mass%, thereby obtaining a carboxyl group-and unsaturated group-containing resin having a weight average molecular weight of 25300 and a solid acid value of 103 KOHmg/g.
< example 7 >
159.1g of propylene glycol monomethyl ether acetate was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and stirred while being replaced with nitrogen, and the temperature was raised to 120 ℃. Subsequently, a radical polymerizable monomer composed of 85.2g of glycidyl methacrylate, 66.0g of tricyclodecanyl methacrylate and 10.4g of styrene, and a mixture of 17.8g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator, PERBUTYL (registered trademark) O, manufactured by NIGHT OIL CRYSTAL Co., Ltd.) and 46.9g of propylene glycol monomethyl ether acetate were added dropwise to the flask from a dropping funnel over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at 120 ℃ for 2 hours to effect copolymerization reaction, thereby producing an epoxy group-containing copolymer solution having a weight average molecular weight of 4000. The total amount of the residual monomers was measured, and the result was 0.5 mass%. Further, the same reaction was repeated, and as a result, the weight average molecular weight was 4200 and the reproducibility of the molecular weight was good. 43.2g of acrylic acid, 0.6g of hydroquinone as a polymerization inhibitor and 0.6g of triphenylphosphine as a catalyst were put into the flask, and the flask was heated at 110 ℃ for 10 hours while blowing low-oxygen air containing nitrogen gas so that the oxygen concentration was 4 to 6 mass%.
Then, it was confirmed that the acid value was 1.0KOHmg/g or less, 59.3g of tetrahydrophthalic anhydride was charged and reacted at 110 ℃ for 2 hours to obtain a carboxyl group-and unsaturated group-containing resin having a weight average molecular weight of 8000 and a solid acid value of 80 KOHmg/g.
< comparative example 1 >
A carboxyl group-containing resin solution having a weight-average molecular weight of 20000 and a solid acid value of 180KOHmg/g was obtained in the same manner as in example 1, except that the reaction temperature was 90 ℃ and the amount of the thermal radical polymerization initiator was 7.0 g. The same reaction was repeated, and as a result, the weight average molecular weight was 16000 and the reproducibility of the molecular weight was not exhibited.
< comparative example 2 >
A carboxyl group-containing resin solution having a weight-average molecular weight of 15000 and a solid acid value of 180KOHmg/g was obtained in the same manner as in example 1, except that the polymerization temperature was 144 ℃ and the amount of the thermal radical polymerization initiator was 0.7 g. The total amount of residual monomers of the polymer solution was measured and found to be as much as 2.5 mass%.
< comparative example 3 >
The reaction was carried out in the same manner as in example 1 except that the reaction temperature was changed to 70 ℃ and the amount of the polymerization initiator was changed to 8.4g, instead of changing the polymerization initiator to t-butyl peroxypivalate (polymerization initiator, PERBUTYL (registered trademark) PV: 10-hour half-life temperature of 55 ℃ C.), to obtain a carboxyl group-containing resin polymer solution having a weight-average molecular weight of 15000 and a solid acid value of 180 KOHmg/g. The same reaction was repeated, and as a result, the weight average molecular weight was 20000 and the reproducibility of the molecular weight was not exhibited.
The results of the above examples and comparative examples are shown in the table.
[ Table 1]
Claims (14)
1. A method of making a resin, comprising:
a step 1 of adding a radical polymerizable monomer and a thermal radical polymerization initiator to a reaction vessel and polymerizing the radical polymerizable monomer at a temperature 20 to 70 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator; and
and a step 3 of polymerizing the monomer by setting the temperature in the reaction vessel to a temperature which is not lower than 20 ℃ lower than the 10-hour half-life temperature of the thermal radical polymerization initiator and which is lower than 20 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator.
2. The method for producing a resin according to claim 1, wherein the radical polymerizable monomer and the thermal radical polymerization initiator are added dropwise into a reaction vessel.
3. The method for producing a resin according to claim 1 or 2, wherein the radical polymerizable monomer and the thermal radical polymerization initiator are added after the temperature in the reaction vessel is set to be 20 to 70 ℃ higher than the 10-hour half-life temperature of the thermal radical polymerization initiator.
4. The method for producing a resin according to claim 1 or 2, comprising: and a step 2 of reacting the radical polymerizable monomer and the thermal radical polymerization initiator for 30 to 300 minutes after the addition of the radical polymerizable monomer and the thermal radical polymerization initiator is completed.
5. The method for producing a resin according to claim 1 or 2, wherein the thermal radical polymerization initiator is a peroxide.
6. The method for producing a resin according to claim 1 or 2, wherein the thermal radical polymerization initiator has a 10-hour half-life temperature of 60 to 110 ℃.
7. The method for producing a resin according to claim 1 or 2, wherein the addition time of the radical polymerizable monomer is 30 to 300 minutes.
8. The method for producing a resin according to claim 1 or 2, wherein in the step 3, the polymerization time is 60 to 300 minutes.
9. The method for producing a resin according to claim 1 or 2, wherein an additional thermal radical polymerization initiator is added in the step 3.
10. The method for producing a resin according to claim 1 or 2, wherein an additional radical polymerizable monomer is added in the step 3.
11. The method for producing a resin according to claim 1 or 2, wherein the radical polymerizable monomer contains (meth) acrylic acid.
12. The method for producing a resin according to claim 11, wherein an unsaturated group is introduced by adding glycidyl (meth) acrylate to a carboxyl group derived from (meth) acrylic acid of the resin.
13. The method for producing a resin according to claim 11, wherein the acid value of the resin is 10 to 300 KOHmg/g.
14. The method for producing a resin according to claim 1 or 2, wherein the weight average molecular weight of the resin in terms of polystyrene is 1000 to 50000.
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| CN1455784A (en) * | 1999-04-30 | 2003-11-12 | 综研化学株式会社 | Process for producing acrylic polymer |
| TW201107349A (en) * | 2009-05-01 | 2011-03-01 | Nissan Chemical Ind Ltd | Method for producing highly branched polymer |
| CN103897096A (en) * | 2012-12-27 | 2014-07-02 | 日本碧化学公司 | Method for producing crosslinked polymer, crosslinked polymer, and coating composition containing the same |
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| JP4704586B2 (en) | 2001-03-13 | 2011-06-15 | 日東電工株式会社 | Method for producing medical acrylic adhesive |
| JP5046151B2 (en) * | 2006-11-30 | 2012-10-10 | 綜研化学株式会社 | Manufacturing method for environmentally friendly adhesives |
| JP2008266555A (en) | 2007-03-23 | 2008-11-06 | Hitachi Chem Co Ltd | Method for manufacturing acrylic copolymer |
| JP2011168749A (en) * | 2010-02-22 | 2011-09-01 | Sekisui Chem Co Ltd | Method of manufacturing thermally expansible microcapsule |
| JP5953094B2 (en) * | 2012-04-11 | 2016-07-20 | 日華化学株式会社 | Method for producing fluorine-containing polymer compound, surface conditioning agent, leveling agent and coating agent |
| JP6279316B2 (en) * | 2012-12-27 | 2018-02-14 | 日本合成化学工業株式会社 | Method for producing acrylic resin for heat-resistant adhesive film |
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| CN1455784A (en) * | 1999-04-30 | 2003-11-12 | 综研化学株式会社 | Process for producing acrylic polymer |
| TW201107349A (en) * | 2009-05-01 | 2011-03-01 | Nissan Chemical Ind Ltd | Method for producing highly branched polymer |
| CN103897096A (en) * | 2012-12-27 | 2014-07-02 | 日本碧化学公司 | Method for producing crosslinked polymer, crosslinked polymer, and coating composition containing the same |
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