KR102623654B1 - Resin manufacturing method - Google Patents

Abstract

The purpose of the present invention is to provide a method for producing a resin using radical polymerization that can obtain sufficient reproducibility of molecular weight and has a small amount of residual monomer. In order to achieve the above object, the present invention includes adding a radically polymerizable monomer and a thermal radical polymerization initiator to a reaction vessel, and carrying out the radical polymerization at a temperature 20 to 70° C. higher than the 10-hour half-life temperature of the thermal radical polymerization initiator. A method for producing a resin comprising polymerizing a monomer is provided.

Description

Resin manufacturing method

The present invention relates to a method for producing a resin obtained by radical polymerization. Specifically, it relates to a method for producing a resin that is carried out at a specific temperature when polymerizing a radically polymerizable monomer using a thermal radical polymerization initiator.

Recently, from the viewpoint of resource saving and energy saving, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays or electron beams have been widely used in various fields such as coatings, printing, paints, and adhesives. Also, in the field of electronic materials such as printed wiring boards, photosensitive resin compositions that can be cured by active energy rays are used in solder resists, color filters, black matrices, photo spacers, resists for protective films, etc.

In the same field, it is known that resins obtained by radical polymerization are used, and various methods for producing resins obtained by general radical polymerization have also been proposed so far (Patent Documents 1 and 2). However, the conventional method for producing a resin obtained by radical polymerization had problems such as insufficient molecular weight reproducibility and mass production, and a large amount of residual monomer.

Japanese Patent Publication No. 2002-265390 Japanese Patent Publication No. 2008-266555

As described above, the conventional method for producing a resin using radical polymerization sometimes lacks reproducibility of molecular weight or has a large amount of residual monomer, making it difficult to mass-produce it industrially.

Therefore, the present invention was made to solve the problems described above, and its purpose is to provide a method for producing a resin using radical polymerization that can obtain sufficient reproducibility of molecular weight and has a small amount of residual monomer.

The present inventors have conducted intensive studies to solve the above problems, and as a result, when polymerizing a radically polymerizable monomer using a thermal radical polymerization initiator, the 10-hour half-life temperature of the thermal radical polymerization initiator is 20 to 70 ° C. It was discovered that the above problem could be solved by setting the temperature at a high temperature, and this led to the present invention.

That is, the present invention:

(1) Adding a radically polymerizable monomer and a thermal radical polymerization initiator to a reaction vessel, and Step 1 of polymerizing the radically polymerizable monomer at a temperature 20 to 70°C higher than the 10-hour half-life temperature of the thermal radical polymerization initiator. Including, a method for producing a resin,

(2) The method for producing the resin of (1), wherein the radical polymerizable monomer and the thermal radical polymerization initiator are added dropwise to a reaction vessel,

(3) The resin of (1) or (2), wherein the inside of the reaction vessel is heated to a temperature of 20 to 70°C higher than the 10-hour half-life temperature of the thermal radical polymerization initiator, and then the radical polymerizable monomer and the thermal radical polymerization initiator are added. manufacturing method,

(4) A method for producing the resin according to any one of (1) to (3), comprising step 2 of reacting for 0.5 to 3 hours after completion of addition of the radical polymerizable monomer,

(5) A method for producing the resin of any one of (1) to (4), wherein the thermal radical polymerization initiator is peroxide,

(6) The method for producing the resin according to any one of (1) to (5), wherein the 10-hour half-life temperature of the thermal radical polymerization initiator is 60 to 110 ° C.

(7) The method for producing the resin according to any one of (1) to (6), wherein the addition time of the radical polymerizable monomer is 60 to 300 minutes,

(8) After completion of Step 1 or Step 2, Step 3 of polymerization by further setting the temperature in the reaction vessel to a temperature between 20°C lower and 20°C higher than the 10-hour half-life temperature of the thermal radical polymerization initiator. A method for producing the resin of any one of (1) to (7), including,

(9) The method for producing the resin of (8), wherein in step 3, the polymerization time is 60 to 300 minutes,

(10) The method for producing the resin of (8) or (9), wherein in step 3, an additional thermal radical polymerization initiator is added,

(11) The method for producing the resin according to any one of (8) to (10), wherein in step 3, an additional radically polymerizable monomer is added,

(12) The method for producing the resin according to any one of (1) to (11), wherein the radically polymerizable monomer contains (meth)acrylic acid,

(13) The method for producing the resin of (12), wherein an unsaturated group is introduced by adding glycidyl (meth)acrylate to the carboxyl group derived from (meth)acrylic acid of the resin,

(14) The method for producing the resin of (12), wherein the acid value of the resin is 10 to 300 KOHmg/g, and

(15) A method for producing the resin according to any one of (1) to (14), wherein the resin has a weight average molecular weight of 1,000 to 50,000 in terms of polystyrene, is provided.

By the production method of the present invention, sufficient reproducibility of molecular weight can be obtained and a resin with few residual monomers can be obtained. Therefore, the production method of the present invention can be used for industrial mass production of resin because of its good reproducibility. In addition, the manufacturing method of the present invention has the advantage that since the remaining monomer is small, the volatilization of the remaining monomer is small when heated in paints using resin, etc., thereby preventing contamination of the manufacturing equipment, etc.

The present invention will be described in detail below.

Polymerization of the radically polymerizable monomer of the present invention can be carried out in a batch operation within a reaction vessel.

The reaction vessel used in the present invention is not particularly limited as long as it is a reaction vessel used industrially to polymerize a radically polymerizable monomer. For example, there is a reaction vessel equipped with a mixing function and a temperature control function, and having a supply port and an outlet through which raw materials can be supplied and the reaction liquid can be taken out.

As a thermal radical polymerization initiator used in the present invention, a thermal radical polymerization initiator that generates thermal radicals by heat is usually used, and both an organic peroxide-based initiator and an azo-based initiator can be used. Preferred organic peroxide-based initiators include, for example, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxycarbonate, and peroxydicarbonate, and among them, hydroperoxide Roperoxide, dialkyl peroxide, diacyl peroxide, and peroxy ester are preferred, and peroxy ester is particularly preferred. Preferred azo initiators include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and methyl 2,2'-azobisisobutyrate. do. These may be used individually, and 2 or more types may be used together.

The 10-hour half-life temperature of the thermal radical polymerization initiator used in the present invention is preferably 60 to 110°C, and more preferably 70 to 100°C.

In addition, the 10-hour half-life temperature refers to the temperature at which the time (half-life) until the concentration of the thermal radical polymerization initiator decreases to half the initial value when dissolved in a solvent is 10 hours. The 10-hour half-life can be calculated using known methods or methods described in known literature. Additionally, when using a commercially available product, the values stated in the catalog or specifications can also 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 amount of polymerizable monomers charged is 100 parts by mass.

＜Process 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 polymerized within the reaction vessel.

The polymerization reaction can be carried out in the presence or absence of a solvent according to a radical polymerization method known in the art. For example, the radical polymerizable monomer may be added and dissolved in a solvent as desired, and the polymerization reaction may be performed together with a thermal radical polymerization initiator at a temperature 20 to 70° C. 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, but since it is easy to control the addition amount, addition speed, and addition time, it is preferable to add them dropwise to the reaction vessel. Additionally, these may be mixed and added as a mixture, or may be added separately.

When adding a radical polymerizable monomer and a thermal radical polymerization initiator to a reaction vessel, either or both can be added by dissolving them in a solvent. At this time, 0 to 100 parts by mass of solvent is mixed with 100 parts by mass of radically polymerizable monomer, preferably 0 to 50 parts by mass, and added to the reaction vessel. Additionally, with respect to 100 parts by mass of the thermal radical polymerization initiator, 100 to 10,000 parts by mass of the solvent is mixed, preferably 150 to 5,000 parts by mass, and added to the reaction vessel. In addition, when adding a mixture of a radical polymerizable monomer and a thermal radical polymerization initiator to the reaction vessel, the solvent is added in an amount of 0 parts by mass to 100 parts by mass, preferably 0 parts by mass to 50 parts by mass, based on 100 parts by mass of the mixture. Mix by mass and add to the reaction vessel.

The time for adding the radically polymerizable monomer is not particularly limited, but is usually added to the reaction vessel over 30 minutes to 300 minutes, preferably 60 minutes to 250 minutes. Likewise, the time for adding the thermal radical polymerization initiator to the reaction vessel is not particularly limited, but is usually added over 30 to 300 minutes, preferably 60 to 250 minutes. Additionally, from the viewpoint of work efficiency, etc., the addition time of the radical polymerizable monomer and the thermal radical polymerization initiator may be adjusted to be the same.

In addition, when adding a mixture of a radical polymerizable monomer and a thermal radical polymerization initiator to the reaction vessel, the time for addition is not limited, but is usually added to the reaction vessel over 30 minutes to 300 minutes, preferably 60 minutes to 250 minutes. Add.

When the radical polymerizable monomer and the thermal radical polymerization initiator are dissolved in a solvent and added to the reaction vessel dropwise, the dropping speed is not particularly limited, but the dropping speed of the radical polymerizable monomer is such that the total amount of the radical polymerizable monomer and solvent is 100. When expressed as mL, it is usually 0.1 mL/min to 5 mL/min, preferably 0.2 mL/min to 4 mL/min. Additionally, the dropping rate of the thermal radical polymerization initiator is usually 0.1 mL/min to 5 mL/min, preferably 0.2 mL/min to 4 mL/min, when the total amount of thermal radical polymerization initiator and solvent is 100 mL. . In addition, the dropping rate when dissolving the radical polymerizable monomer and the thermal radical polymerization initiator in a solvent as a mixture and adding it to the reaction vessel is usually 100 ml when the total amount of the radical polymerizable monomer, the thermal radical polymerization initiator, and the solvent is 100 ml. 0.1 mL/min to 5 mL/min, preferably 0.2 mL/min to 4 mL/min.

When carrying out the polymerization reaction, the temperature in the reaction vessel is set to 20 to 70°C, preferably 30 to 60°C higher than the 10-hour half-life temperature of the thermal radical polymerization initiator used, and the reaction is carried out. If the reaction is carried out within this temperature range, the amount of residual monomer can be sufficiently reduced, and the reproducibility of resin production is also excellent. Although the temperature may fluctuate during the polymerization reaction as long as it is within this temperature range, it is preferable to carry out the reaction at a constant temperature from the viewpoint of work efficiency. When using two or more types of thermal radical polymerization initiators, the polymerization reaction is performed by selecting a temperature that is 20 to 70°C higher than the 10-hour half-life temperature of all thermal radical polymerization initiators.

In addition, from the viewpoint of carrying out the polymerization reaction efficiently, the temperature in the reaction vessel is 20 to 70 ° C 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. It is desirable to adjust it to .

＜Process 2＞

After the radical polymerizable monomer and the thermal radical polymerization initiator are added to the reaction vessel, the polymerization reaction is performed at a temperature 20 to 70° C. higher than the 10-hour half-life temperature of the thermal radical polymerization initiator. The time for this polymerization reaction is not particularly limited, but is usually 30 minutes to 300 minutes, preferably 30 minutes to 180 minutes. The polymerization reaction here is preferably carried out while stirring.

＜Process 3＞

After the polymerization reaction is performed at a temperature 20 to 70°C higher than the 10-hour half-life temperature, an additional polymerization reaction may be performed at a temperature ranging from 20°C lower to 20°C higher than the 10-hour half-life temperature. Additionally, by carrying out this polymerization reaction, the amount of remaining monomer can be further reduced.

In step 3, a thermal radical polymerization initiator or a radical polymerizable monomer may be further added. The thermal radical polymerization initiator species added during this additional polymerization reaction may be the same as or different from that used during the polymerization reaction in Step 1.

If the thermal radical polymerization initiator added in Step 1 and Step 3 is different, the polymerization reaction is performed by selecting a temperature range from 20°C lower to 20°C higher than the 10-hour half-life temperature of all thermal radical polymerization initiators. .

Also, in this case, the thermal radical polymerization initiator can be optionally dissolved in a solvent and added to the reaction vessel by dropping or the like. From the viewpoint of shortening the resin production time and increasing production efficiency, it is preferable to add the thermal radical polymerization initiator to the reaction vessel at once during the additional polymerization reaction.

In step 3, when adding a thermal radical polymerization initiator, the amount used is not particularly limited, but is generally 0.5 to 20 parts by mass, preferably 1 part, when the total amount of polymerizable monomer charged is 100 parts by mass. ~10 parts by mass.

In step 3, when adding a radically polymerizable monomer, it may be of the same type or different from the radically polymerizable monomer used in the first polymerization reaction. Additionally, two or more types of radically polymerizable monomers can be used.

In this case, the radically polymerizable monomer can be optionally dissolved in a solvent and added to the reaction vessel dropwise or all at once. From the viewpoint of shortening the resin production time and increasing production efficiency, it is preferable to add the radical polymerizable monomer added in step 3 to the reaction vessel at once.

The reaction time of step 3 is not particularly limited, but is usually 60 to 300 minutes, preferably 120 to 240 minutes. When adding the thermal radical polymerization initiator and/or radical polymerizable monomer to the reaction vessel dropwise, the reaction may be allowed to proceed for usually 60 to 300 minutes, preferably 120 to 240 minutes, after completion of the dropwise addition. In addition, after completion of step 3, it is preferable to process for 30 to 600 minutes at a temperature 20 to 70°C higher than the 10-hour half-life temperature of the thermal radical polymerization initiator.

The radically polymerizable monomer used in the polymerization reaction of the present invention is not particularly limited and includes norbornene and dicyclopentadiene, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o -Chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene, etc. Aromatic vinyl compound;

Conjugated diene compounds such as butadiene, isoprene, and chloroprene;

Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, iso-butyl (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, perfluoro-iso-propyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclofentanyl (meth)acrylate, isobornyl (meth)acrylate, adaman Tyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, triphenylmethyl (meth)acrylate, phenyl (meth)acrylate, cumyl (meth)acrylate, 4-phenok Cyphenyl (meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, n-pentyl methacrylate, isoamyl acrylate, n-hexyl methacrylate , 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, n-octyl methacrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, methoxy-triethylene glycol acrylate, Toxy-diethylene glycol acrylate, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylate (Product name: AM-90G, manufactured by Shinnakamura Chemical Industries, Ltd.), 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate Latex, glycerin mono(meth)acrylate, phenoxyethyl acrylate, phenoxy-polyethylene glycol acrylate (Product name: Light Acrylate P-200A, manufactured by Kyoei Chemical Co., Ltd.), o-phenoxybenzyl acrylate, m-phenocrylate Cibenzyl acrylate, p-phenoxybenzyl acrylate, reaction product of (meth)acryloyloxyethylisocyanate (i.e. 2-isocyanatoethyl(meth)acrylate) and ε-caprolactam, (meth)acrylate Reaction product of monooxyethyl isocyanate and propylene glycol monomethyl ether, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, glycidyl(meth)acrylate, 2-glycidyloxyethyl(meth) Acrylates, 3,4-epoxycyclohexylmethyl (meth)acrylate and lactone adducts (e.g., Cychroma A200, M100 manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl- Mono(meth)acrylic acid ester of 3',4'-epoxycyclohexanecarboxylate, epoxidized product of dicyclopentenyl(meth)acrylate, epoxidized product of dicyclopentenyloxyethyl(meth)acrylate, etc. Meth)acrylic acid ester compound;

Carboxyl group-containing ethylenically unsaturated compounds such as (meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, and maleic acid, and substituents thereof;

(meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di - (meth)acrylic acid amides such as isopropylamide and (meth)acrylic acid anthracenylamide;

Vinyl compounds such as (meth)acrylic acid anilide, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyl toluene;

Unsaturated dicarboxylic acid diester compounds such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconate;

Monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide;

etc. can be mentioned. These radically polymerizable monomers can be used individually or in mixture of two or more types. Among these, from the viewpoint of applying the resin to various resists, it is preferable to use at least an ethylenically unsaturated compound containing a carboxyl group, and it is more preferable to use (meth)acrylic acid.

Solvents that can be used in this polymerization reaction are not particularly limited, but examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monomethyl ether. -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, di (Poly)alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether. compound;

(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 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl- 3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-propionate. Ester compounds such as butyl, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, 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,N-dimethylformamide, and N,N-dimethylacetamide; etc. can be mentioned. These solvents can be used individually or in mixture of two or more types.

Among these, (poly)alkylene glycol ether-based solvents such as (poly)alkylene glycol monoalkyl ether compounds and (poly)alkylene glycol monoalkyl ether acetate compounds are preferable, and propylene glycol monomethyl ether and propylene glycol monomethyl Propylene glycol-based solvents such as ether acetate are more preferable.

The total amount of solvent used for the polymerization reaction of the present invention is not particularly limited, but is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass, when the total amount of radical polymerizable monomer charged is 100 parts by mass. . In particular, by setting the amount of solvent used to 1,000 parts by mass or less, a decrease in the molecular weight of the polymer due to chain transfer action can be suppressed, and the viscosity of the polymer can be controlled to an appropriate range. Moreover, by setting the compounding amount of the solvent to 30 parts by mass or more, abnormal polymerization reaction can be prevented and polymerization reaction can be carried out stably, and coloring and gelation of the polymer can also be prevented.

When applying the present invention 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 at least a carboxyl group-containing ethylenically unsaturated compound as a radically polymerizable monomer. Additionally, it can also be obtained by the denaturation method (I) below. The polymerizable unsaturated bond is obtained, for example, by carrying out the modification reaction (II) below.

(I) Denaturation method:

As a radically polymerizable monomer, an ethylenically unsaturated compound containing an epoxy group such as glycidyl (meth)acrylate is used. The epoxy group contained in the molecule of the resin obtained by radical polymerization is cleaved with a polymerizable unsaturated monobasic acid such as (meth)acrylic acid, and the hydroxy group produced by the cleavage is reacted with the polybasic acid or its anhydride.

When using the modification method (I) described above, the reaction between the resin obtained by the method of the present invention and the adduct can be carried out according to a conventional method. After the polymerization reaction is completed, the modification reaction can be performed without removing the solvent, for example, by adding a polymerizable unsaturated monobasic acid to the reaction solvent containing the resin, and further adding a polymerization inhibitor and a catalyst. After reacting at, for example, 50 to 150°C, preferably 80 to 130°C, the polybasic acid or its anhydride may be further added and the reaction may be carried out at 50 to 150°C, preferably 80 to 130°C. Examples of the polybasic acid or its anhydride include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and succinic anhydride.

(II) Denaturation method:

As the radically polymerizable monomer, at least an ethylenically unsaturated compound containing a carboxyl group is used. 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 (II), as in the case of the modification method (I), the modification reaction can be carried out without removing the solvent after the polymerization reaction in the production method of the present invention is completed, and the modification reaction of the present invention can be carried out without removing the solvent. A (meth)acrylate monomer having a carboxyl group and a reactive functional group and a catalyst are added to the reaction solvent containing the resin obtained by the method, and if necessary, a polymerization inhibitor is added to prevent gelation, and the temperature is preferably 50 to 150°C. Preferably, the reaction may be performed at 80 to 130°C.

When the resin obtained by the production method of the present invention has an acid group, its acid value (JIS K6901 5.3) can be appropriately selected, but when used as a photosensitive polymer, it is usually 10 to 300 KOHmg/g, preferably 20 to 200 KOHmg. The range is /g.

In addition, the weight average molecular weight of the resin obtained in the present invention can be adjusted according to the application, but when used for various resist materials, it is preferably 1,000 to 50,000, and 3,000 to 40,000 from the viewpoint of improved heat yellowing resistance and improved developability. It is more preferable to be

In addition, the weight average molecular weight in the present invention means the weight average molecular weight in terms of standard polystyrene measured under the following conditions using gel permeation chromatography (GPC).

Column: Showex (registered trademark) LF-804+LF-804 (manufactured by Showa Electric Co., Ltd.)

Column temperature: 40℃

Sample: 0.2% by mass tetrahydrofuran solution of copolymer

Development solvent: tetrahydrofuran

Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Electric Co., Ltd.)

Flow rate: 1 mL/min

The photosensitive resin composition containing the polymerizable resin obtained from the resin produced in the present invention is used in various resists, especially color filters, black matrices, photo spacers, protective films, and overcoats mounted on organic EL displays, liquid crystal displays, and solid-state imaging devices. It is suitable for use as a resist used to manufacture.

Example

Examples and comparative examples are given below to explain the present invention in detail.

The amount of residual monomer in the following examples and comparative examples was measured using GPC under the conditions described above, in the same manner as the measurement of the weight average molecular weight.

In addition, the reproducibility of the weight average molecular weight was judged based on the following standards.

Judgment criteria for reproducibility

○: The same polymerization reaction is repeated twice, and the rate of change in the weight average molecular weight for the second time ((weight average molecular weight for the second time - weight average molecular weight for the first time)/weight average molecular weight for the first time × 100) is within ±10%.

×: The same polymerization reaction was repeated twice, and the rate of change in weight average molecular weight the second time was outside the range of ±10%.

<Example 1>

128.8 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, stirred while purging with nitrogen, and raised the temperature to 120°C.

Next, a radically polymerizable monomer consisting of 38.7 g of methacrylic acid, 22.0 g of tricyclodecanyl methacrylate, and 79.2 g of benzyl methacrylate, 79.3 g of propylene glycol monomethyl ether acetate, and 2.0 g of t-butyl peroxy. -2-Ethylhexanoate (thermal radical polymerization initiator, manufactured by Nichiyu Corporation, Perbutyl (registered trademark) O: 10 hour half-life temperature, 72°C) was mixed and added dropwise into the flask separately over 2 hours from a dropping funnel. did. After completion of the dropwise addition, the mixture was stirred at 120°C for another 2 hours to perform a polymerization reaction, thereby obtaining a carboxyl group-containing resin solution with a weight average molecular weight of 17,500 and a solid acid value of 180 KOHmg/g.

The total amount of remaining monomer was measured and found to be 0.8% by mass. In addition, as a result of performing the same reaction again, the weight average molecular weight was 18,000, and the reproducibility of the molecular weight was good.

<Example 2>

The thermal radical polymerization initiator was changed to 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (manufactured by Nichi Yu Co., Ltd., Perocta (registered trademark) O: 10 hours half-life temperature 65°C), and reaction was carried out. The reaction was performed in the same manner except that the temperature was 109°C, and a carboxyl group-containing resin solution with a weight average molecular weight of 18,500 and a solid acid value of 180 KOHmg/g was obtained. The total amount of remaining monomer was measured and found to be 0.7% by mass. Additionally, as a result of performing the same reaction again, the weight average molecular weight was 19,300, showing good molecular weight reproducibility.

<Example 3>

The reaction was carried out in the same manner except that the thermal radical polymerization initiator was changed to t-butylperoxybenzoate (Nippon Kayaku Co., Ltd., Kayabutyl B (registered trademark): 10-hour half-life temperature: 105°C), and the reaction temperature was set to 127°C. This was performed to obtain a carboxyl group-containing resin solution with a weight average molecular weight of 14,800 and a solid acid value of 180 KOHmg/g. The total amount of remaining monomer was measured and found to be 0.6% by mass. In addition, as a result of performing the same reaction again, the weight average molecular weight was 15,100, and the reproducibility of the molecular weight was good.

<Example 4>

In the solution of Example 1, 2.8 g of propylene glycol monomethyl ether acetate and 0.7 g of t-butylperoxy-2-ethylhexanoate (thermal radical polymerization initiator, manufactured by Nichiyu Corporation, Perbutyl (registered trademark) O: 10 hours (half-life temperature: 72°C) was added to the flask, and reaction was performed at 90°C for 3 hours (step 3) to obtain a carboxyl group-containing resin solution with a weight average molecular weight of 17,300 and a solid acid value of 180 KOH mg/g.

<Example 5>

The reaction was carried out in the same manner as in Example 1 except that the amount of methacrylic acid was changed to 37.0 g, and a carboxyl group-containing resin solution with a weight average molecular weight of 17,300 and a solid acid value of 180 KOHmg/g was obtained.

Additionally, 2.8 g of propylene glycol monomethyl ether acetate and 0.7 g of t-butylperoxy-2-ethylhexanoate (thermal radical polymerization initiator, manufactured by Nichi Yu Co., Ltd., perbutyl (registered trademark) O: 10 hours half-life temperature 72°C) , 1.7 g of methacrylic acid was added to the flask, and reaction was performed at 90°C for 3 hours to obtain a carboxyl group-containing resin solution with a weight average molecular weight of 17,100 and a solid acid value of 180 KOHmg/g.

<Example 6>

To the solution of Example 4, 21.3 g of glycidyl methacrylate, 0.5 g of hydroquinone as a polymerization inhibitor, and 0.5 g of triphenylphosphine as a catalyst were added, and nitrogen gas was added so that the oxygen concentration was 4% by mass to 6% by mass. was heated at 110°C for 10 hours while blowing low-oxygen air to obtain a carboxyl group- and unsaturated group-containing resin with a weight average molecular weight of 25,300 and a solid acid value of 103 KOHmg/g.

<Example 7>

159.1 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, stirred while purging with nitrogen, and raised the temperature to 120°C. Next, a radically polymerizable monomer consisting of 85.2 g of glycidyl methacrylate, 66.0 g of tricyclodecanyl methacrylate, and 10.4 g of styrene, and 46.9 g of propylene glycol monomethyl ether acetate plus 17.8 g of t-butyl peroxy. -2-Ethylhexanoate (polymerization initiator, manufactured by Nichiyu Corporation, Perbutyl (registered trademark) O) was added dropwise from a dropping funnel into the flask separately over 2 hours. After completion of the dropwise addition, the copolymerization reaction was performed by stirring at 120°C for an additional 2 hours to produce an epoxy group-containing copolymer solution with a weight average molecular weight of 4,000. The total amount of remaining monomer was measured and found to be 0.5% by mass. In addition, as a result of performing the same reaction again, the weight average molecular weight was 4,200, and the reproducibility of the molecular weight was good. 43.2 g of acrylic acid, 0.6 g of hydroquinone as a polymerization inhibitor, and 0.6 g of triphenylphosphine as a catalyst were injected into it, and low-oxygen air containing nitrogen gas was blown so that the oxygen concentration was 4% by mass to 6% by mass. It was heated at 110°C for 10 hours.

After that, it was confirmed that the acid value was 1.0 KOHmg/g or less, and 59.3 g of tetrahydrophthalic anhydride was added and reacted at 110°C for 2 hours to produce a carboxyl group- and unsaturated group-containing resin with a weight average molecular weight of 8,000 and a solid acid value of 80 KOHmg/g. got it

<Comparative Example 1>

A carboxyl group-containing resin solution with a weight average molecular weight of 20,000 and a solid acid value of 180 KOHmg/g was obtained in the same manner as in Example 1 except that the reaction temperature was 90°C and the amount of thermal radical polymerization initiator was 7.0 g. As a result of performing the same reaction again, the weight average molecular weight was 16,000, and there was no reproducibility of the molecular weight.

<Comparative Example 2>

A carboxyl group-containing resin solution with a weight average molecular weight of 15,000 and a solid acid value of 180 KOHmg/g was obtained in the same manner as in Example 1 except that the polymerization temperature was 144°C and the amount of thermal radical polymerization initiator was 0.7 g. The total amount of monomers remaining in the polymer solution was measured and found to be as high as 2.5% by mass.

<Comparative Example 3>

Except that the reaction temperature was changed to 70°C and the polymerization initiator was t-butylperoxypivalate (polymerization initiator, manufactured by Nichiyu Corporation, perbutyl (registered trademark) PV: 10 hour half-life temperature: 55°C), and the amount was changed to 8.4 g. The reaction was carried out in the same manner as in Example 1 to obtain a carboxyl group-containing resin polymer solution with a weight average molecular weight of 15,000 and a solid acid value of 180 KOHmg/g. As a result of performing the same reaction again, the weight average molecular weight was 20,000, and there was no reproducibility of the molecular weight.

The results of the above examples and comparative examples are shown in the table.

Claims (15)

Step 1 of adding a radically polymerizable monomer and a thermal radical polymerization initiator to a reaction vessel, and polymerizing the radically polymerizable monomer at a temperature 20 to 70°C higher than the 10-hour half-life temperature of the thermal radical polymerization initiator,
Additionally, a method for producing a resin comprising step 3 of polymerizing the temperature in the reaction vessel by setting it to a temperature between 20°C lower than 20°C and lower than 20°C higher than the 10-hour half-life temperature of the thermal radical polymerization initiator. According to claim 1,
A method for producing a resin, wherein the radically polymerizable monomer and the thermal radical polymerization initiator are added dropwise to a reaction vessel. The method of claim 1 or 2,
A method for producing a resin, wherein the inside of the reaction vessel is heated to a temperature of 20 to 70°C higher than the 10-hour half-life temperature of the thermal radical polymerization initiator, and then a radical polymerizable monomer and a thermal radical polymerization initiator are added. The method of claim 1 or 2,
A method for producing a resin, comprising step 2 of reacting for 30 to 300 minutes after completion of addition of the radical polymerizable monomer and the thermal radical polymerization initiator. The method of claim 1 or 2,
A method for producing a resin, wherein the thermal radical polymerization initiator is peroxide. The method of claim 1 or 2,
A method for producing a resin, wherein the 10-hour half-life temperature of the thermal radical polymerization initiator is 60 to 110 ° C. The method of claim 1 or 2,
A method for producing a resin, wherein the addition time of the radical polymerizable monomer is 30 minutes to 300 minutes. The method of claim 1 or 2,
A method for producing a resin in Step 3, wherein the polymerization time is 60 to 300 minutes. The method of claim 1 or 2,
A method for producing a resin, wherein in step 3, an additional thermal radical polymerization initiator is added. The method of claim 1 or 2,
A method for producing a resin, wherein in step 3, an additional radically polymerizable monomer is added. The method of claim 1 or 2,
A method for producing a resin, wherein the radically polymerizable monomer contains (meth)acrylic acid. According to claim 11,
A method for producing a resin, wherein an unsaturated group is introduced by adding glycidyl (meth)acrylate to the carboxyl group derived from (meth)acrylic acid of the resin. According to claim 11,
A method for producing a resin wherein the acid value of the resin is 10 to 300 KOHmg/g. The method of claim 1 or 2,
A method for producing a resin, wherein the weight average molecular weight of the resin in terms of polystyrene is 1,000 to 50,000. delete