JP2001081149A - Production of radical-polymerizable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing the subject resin composition slight in viscosity increase and gelled matter formation compared with conventional methods by bulk polymerization, easy to conduct a temperature control of the contents, and advantageous in all of the aspects about time, operation and energy compared with conventional solution polymerization. SOLUTION: This method comprises the following step: a polymerizable monomer A having in one molecule one cationically polymerizable reactive group A1 is put to cationic polymerization in a reactive medium, i.e., a liquid polymerizable monomer B having in one molecule at least one reactive group B1 having substantial radical polymerizability but no cationic polymerizability to produce the objective radical-polymerizable resin composition comprising the monomer B and the polymer made from the above monomer A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a radically polymerizable resin composition containing a polymer and a radically polymerizable monomer. More specifically, the present invention relates to a method for easily producing a radically polymerizable resin composition in one step.

[0002]

2. Description of the Related Art Conventionally, when producing a radically polymerizable resin composition (syrup) in which a polymer is dissolved in a liquid radically polymerizable monomer, the polymer is produced by solution polymerization or bulk polymerization, and this is then produced. A method of dissolving in a radical polymerizable monomer has been adopted. When a polymer is produced by solution polymerization, a step of devolatilizing the solvent and a step of re-diluting it into a radical polymerizable monomer are necessary, so that the production steps are many and complicated. In addition, when a polymer is produced by bulk polymerization, there are problems that a viscosity rise and a gel occur during the production, and it is difficult to remove heat generated by polymerization.

When a polymer having a double bond in a side chain is produced, a cross-linked structure is formed even if polymerization is carried out using a monomer having two or more double bonds. No double bond remains. Therefore, first, a polymer having a carboxyl group or the like in the side chain is obtained, and then a group capable of reacting with the carboxyl group and a compound having a double bond (glycidyl (meth) acrylate or the like) are reacted to form a double bond in the side chain. A bond had to be introduced.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to reduce the increase in viscosity and the generation of gels as compared with a conventional method for producing a radically polymerizable resin by bulk polymerization.
It is another object of the present invention to provide a method for producing a radically polymerizable resin composition that can easily control the temperature of contents and is advantageous in all aspects of time, operation, and energy as compared with conventional solution polymerization.

[0005]

In order to solve the above-mentioned problems, a method for producing a radically polymerizable resin composition according to the present invention comprises:
A method for producing a radically polymerizable resin composition containing a polymer and a radically polymerizable monomer, the polymerizable monomer having one cationically polymerizable reactive group (A1) in one molecule (A) is reacted with a liquid polymerizable monomer (B) having at least one reactive group (B1) having at least one radically polymerizable and not cationically polymerizable in one molecule as a reaction medium. To obtain a radical polymerizable resin composition containing a polymer having the polymerizable monomer (A) as an essential monomer component and the polymerizable monomer (B). .

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The most characteristic feature of the present invention is that cationic polymerization of a cationically polymerizable monomer is carried out using a radically polymerizable monomer as a reaction medium. Since the reaction product thus obtained contains a polymer produced by cationic polymerization and a radically polymerizable monomer as a reaction medium, a radically polymerizable resin composition can be easily obtained in one step. Can be.

In the present invention, the term "cationically polymerizable" refers to the property of cationically polymerizing by irradiation with active energy rays such as heat, ultraviolet rays, and electron beams in the presence of a cationic polymerization initiator. It refers to the property of undergoing radical polymerization by irradiation with active energy rays such as heat, ultraviolet rays, and electron beams in the presence or absence of an initiator.

The polymerizable monomer (A) having one cationically polymerizable reactive group (A1) in one molecule includes one cationically polymerizable reactive group (A) in one molecule. It may be a polymerizable monomer (C) having C1) and at least one reactive group having radical polymerizability (C2), or a monomer having one cationic polymerizability in one molecule. It may be a polymerizable monomer (D) having a group (D1) and having no reactive group having radical polymerizability.

The cationically polymerizable reactive group (A)
1), (C1) and (D1) may be those having cationic polymerizability, and may be those having radical polymerizability or those not having it.
Specifically, at least one selected from the group consisting of a group having a vinylamino group, a vinylamide group, a styryl group, an allyl group, a vinyl ether group, an epoxy ring, an oxetane ring, a cyclic ether group, an aziridine ring, a cyclic sulfide, and a lactone ring. Preferably it is a seed. Among them, at least one selected from the group consisting of a vinyl ether group, a styryl group, an epoxy ring, and a lactone ring is particularly preferable.

Reactive group having radical polymerizability (C2)
Has radical polymerizability and very low cationic polymerizability. Very low cationic polymerizability,
Specifically, any material that does not exhibit cationic polymerizability by itself may be used. That is, the reactive group (C2) having radical polymerizability may be capable of cationic polymerization in the presence of the reactive group having cationic polymerizability. Only very small amounts can be copolymerized. Reactive group having radical polymerizability (C2)
Specifically, at least one selected from the group consisting of a (meth) acryloyl group, a (meth) acrylamide group, a maleate group, a fumarate group and a maleimide group
Preferably it is a seed. Among them, it is particularly preferable that at least one selected from the group consisting of a (meth) acryloyl group, a (meth) acrylamide group, and a maleimide group is used.

The number of reactive groups (A1) having cationic polymerizability of the polymerizable monomer (A) is one. This is because a polymer having a crosslinked structure can be obtained when the compound has two or more reactive groups (A1). The number of reactive groups (C2) having radical polymerizability of the polymerizable monomer (C) is at least one, and when two or more, they may be the same or different.

Specific examples of the polymerizable monomer (C) include compounds having an epoxy ring such as glycidyl (meth) acrylate and a (meth) acryloyl group; allyl groups such as allyl (meth) acrylate and (meth) acryloyl. Compound having a cyclic ether group such as tetrahydrofurfuryl (meth) acrylate and a (meth) acryloyl group; compound having an allyl group and a (meth) acryloyl group such as dicyclopentenyl (meth) acrylate; Compounds having a dioxolane ring (cyclic ether group) such as (meth) acryloyl-1,3-dioxolane and a (meth) acryloyl group are exemplified.

Specific examples of the polymerizable monomer (D) include N
-A compound having a vinylamino group such as vinylimidazole; a compound having a vinylamide group such as N-vinylformamide or N-vinylpyrrolidone: a compound having a styryl group such as α-methylstyrene or indene; or an allyl group such as allylbenzene. Compound having a vinyl ether group such as isobutyl vinyl ether; Compound having an epoxy ring such as n-butyl glycidyl ether; Compound having an oxetane ring such as hexyl oxetane used in Examples described later; 2-methylaziridine and the like Compounds having an aziridine ring; compounds having a cyclic sulfide such as propylene sulfide; and compounds having a lactone ring such as β-propiolactone.

As the polymerizable monomer (A), one or more polymerizable monomers (C) may be used, and one or more polymerizable monomers (D) may be used. The polymerizable monomers (C) and (D) may be used in combination. When the polymerizable monomers (C) and (D) are used in combination, the ratio of use thereof is not particularly limited, and they can be mixed at any ratio. However, in consideration of the physical properties of the cured product of the resin composition obtained by the production method of the present invention, particularly the balance between mechanical strength and heat resistance, the total weight of the polymerizable monomers (C) and (D) is 20-80% by weight of polymerizable monomer (C)
And more preferably 30 to 70% by weight. When the amount of the polymerizable monomer (C) used is less than the above range, the heat resistance of the cured product is reduced, and its use is limited. If the amount of the polymerizable monomer (D) is less than the above range, the cured product becomes hard and brittle, and it is difficult to obtain desired physical properties.

The polymerizable monomer (B) is a reaction medium in the cationic polymerization of the polymerizable monomer (A), and functions as a radical polymerizable monomer in the resin composition obtained by the polymerization. Things. In order to be a reaction medium, it must be liquid and capable of dissolving or dispersing the polymerizable monomer (A). In order to function as a radically polymerizable monomer in the resin composition obtained by polymerization, it must not be copolymerized during the cationic polymerization of the polymerizable monomer (A). It is necessary to have a reactive group (B1) having no cationic polymerizability. Of course, it must not have a reactive group having cationic polymerizability.

The reactive group (B1) having substantially radical polymerizability and not having cationic polymerizability has radical polymerizability like the reactive groups (C2) and (D2) having radical polymerizability. In addition, they are very low in cation polymerizability, and specifically, may be those which do not show cation polymerizability by themselves. Specifically, it is preferably at least one selected from the group consisting of a (meth) acryloyl group, a (meth) acrylamide group, a maleate group, a fumarate group and a maleimide group. Among them, at least one selected from the group consisting of a (meth) acryloyl group and a maleimide group is particularly preferable.

As the polymerizable monomer (B), specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) Compounds having a (meth) acryloyl group such as 2-ethylhexyl acrylate; compounds having a fumarate group such as dibutyl fumarate; compounds having a (meth) acrylamide group such as (meth) acrylamide; and maleate groups such as diethyl maleate Compound having a compound having a maleimide group such as N-ethylmaleimide. One or more of these polymerizable monomers (B) can be used.

The polymerizable monomer (A) and the polymerizable monomer (B)
The use ratio of the polymerizable monomer (A) is 5 to 80% by weight based on the total weight of the polymerizable monomers (A) and (B),
It is preferable that the polymerizable monomer (B) is 95 to 20% by weight, more preferably the polymerizable monomer (A) is 10 to 8% by weight.
0% by weight, 90 to 20% by weight of the polymerizable monomer (B), more preferably 20 to 70% by weight of the polymerizable monomer (A), and 80 to 30% by weight of the polymerizable monomer (B). %, More preferably 30 to 70% by weight of the polymerizable monomer (A) and 70 to 30% by weight of the polymerizable monomer (B). That is,
The content of the polymer comprising the polymerizable monomer (A) in the resin composition of the present invention is preferably from 5 to 80% by weight,
-80% by weight is more preferable, 20-70% by weight is further preferable, and 30-70% by weight is further preferable. If the amount of the polymerizable monomer (A) is less than the above range, the cured product becomes hard and brittle, and it is difficult to obtain desired physical properties. If the amount of the polymerizable monomer (B) used is less than the above range, the viscosity of the resin composition portion becomes too high, and the workability may be significantly reduced.

The polymerizable monomer (A) is replaced with the polymerizable monomer (B)
Is used as a reaction medium to obtain a radical polymerizable resin composition containing a polymer composed of the polymerizable monomer (A) and the polymerizable monomer (B). When the polymerizable monomer (B) dissolves the polymer composed of the polymerizable monomer (A) (when the polymerizable monomer (B) is a reaction solvent), the resulting radical polymerizable The resin composition is liquid and transparent. When the polymerizable monomer (B) disperses a polymer composed of the polymerizable monomer (A) (when the polymerizable monomer (B) is a reaction dispersion medium), the obtained radical polymerization is performed. The conductive resin composition becomes cloudy.

The cationic polymerization of the polymerizable monomer (A) can be carried out in the same manner as in the prior art, except that the polymerizable monomer (B) is used as a reaction medium. Examples of the cationic polymerization initiator that can be used at this time include protonic acids such as perchloric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, trichloroacetic acid, and trifluoroacetic acid; boron trifluoride, aluminum bromide, aluminum chloride, Antimony pentachloride, 2nd chloride
Lewis acids such as iron, tetrachloride, titanium tetrachloride, mercury chloride and zinc chloride; and others include iodine and triphenylchloromethane. Among them, boron trifluoride and p-toluenesulfonic acid are preferred.

In the cationic polymerization, a radical polymerization inhibitor may be added at least at the beginning, during or after the polymerization to such an extent that the physical properties of the resin composition obtained later are not impaired. To the obtained radically polymerizable resin composition, preferably, a radical polymerization initiator is added, and at room temperature, by heating, or by irradiating an active energy ray such as an ultraviolet ray or an electron beam, radical polymerization can be performed. . The radical polymerization can be performed in the same manner as in the conventional case.

Examples of the radical polymerization initiator include azo-based compounds such as azobisisobutyronitrile and azobisisovaleronitrile; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, di- tert-
Organic peroxides such as butyl peroxide, tert-butyl perbenzoate, and cyclohexanone peroxide can be used.

In addition to the above radical polymerization initiator, it is also possible to use a so-called photoradical polymerization initiator which generates radical species by the action of light to initiate polymerization. Examples of the photo-radical polymerization initiator include acetophenone-based compounds such as diethoxyacetophenone and 2-hydroxy-2-phenyl-1-phenylpropan-1-one; benzoin-based compounds such as benzoin, benzoin ethyl ether and benzyldimethyl ketal; benzophenone ,
Benzophenone compounds such as benzoylbenzoic acid and methyl benzoylbenzoate; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone and 2-methylthioxanthone; ketones such as α-acyloxime ester, methylphenylglyoxylate, benzyl and camphorquinone 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,
Imidazole compounds such as 2'-imidazole; 2,
Acylphosphine oxide compounds such as 4,6-trimethylbenzoyldiphenylphosphine oxide; and other carbazole compounds can be used.

These radical polymerization initiators and / or photoradical polymerization initiators may be used alone or in combination.
It may be used in combination of more than one kind. The amount of the radical polymerization initiator and / or the photo-radical polymerization initiator used is
Usually 0.1 to 30% by weight based on the total weight of the resin composition
Is used. When the polymerizable monomer (C) is used as at least a part of the polymerizable monomer (A), the polymer composed of the polymerizable monomer (A) becomes a radically polymerizable reactive group (C2 ) (For example, a (meth) acryloyl group) in the side chain. As described above, in the related art, when producing a polymer having a double bond in a side chain, first, a polymer having a carboxyl group or the like in a side chain is obtained, and then a group capable of reacting with the carboxyl group is obtained. It was necessary to introduce a double bond into the side chain by reacting a compound having a double bond (such as glycidyl (meth) acrylate). In contrast, according to the production method of the present invention, a polymer having a double bond (such as a (meth) acryloyl group) in a side chain can be produced in one step.

The radical polymerizable resin composition obtained according to the present invention may contain various additional components, if necessary. As the additional components, including the above-described radical polymerization initiator, for example, a plasticizer such as dibutyl phthalate, methyl methacrylate, acrylates such as butyl acrylate and other diluents, talc, calcium carbonate, silica, a filler such as mica, Titanium oxide, carbon black, pigments such as phthalocyanine blue, thixotropic agents,
Examples include a foaming agent, an antioxidant, an ultraviolet absorber, and a lubricant.

The radical polymerizable resin composition obtained by the present invention can be used for various FRP molded articles, casting, buttons, decorative board resins, or insulating varnishes, similarly to conventionally known radical polymerizable resin compositions. Resin, wood, paper, particle board, metal, plastic, glass, concrete, asphalt, ceramic, coating materials for various base materials, coating materials for civil engineering and construction, coating resins, putty, sealing agents, adhesives, chemical anchors, It can be used as a printing ink binder, a resin for stereolithography, a resin for a solder resist, a resin for a photoresist, a resin for a printing plate, and the like.

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified. [Example 1] stirrer, condenser, dropping funnel, thermometer, dry N ₂ / Air (oxygen content 7%) inlet tube into a four-necked flask equipped with, methyl methacrylate 60 parts and 3 trifluoride of dehydrated and purified 4 parts of boron fluoride ether complex, 50 ° C
Was heated. Next, 140 parts of dehydrated and purified n-butyl glycidyl ether was added dropwise over 1 hour, and after completion of the addition, the internal temperature was raised to 80 ° C., maintained at the same temperature for 6 hours, and then cooled to obtain a radical polymerizable resin composition (I). I got The reaction was kept in a uniform state throughout, and no production problems such as poor stirring and difficulty in controlling the internal temperature were observed.

The obtained resin composition has a viscosity of 730 at 25 ° C.
cp, a pale yellow transparent liquid having a resin solid content of 70% as measured by non-volatile content and n as determined by gas chromatography.
-The residual amount of butyl glycidyl ether was 0.01%. The molecular weight of the resin solids measured by gel permeation chromatography is the number average molecular weight (M
n) = 2700 and weight average molecular weight (Mw) = 4300. Example 2 A four-necked flask equipped with a stirring rod, a cooling tube, a dropping funnel, a thermometer, and a dry N ₂ / Air (oxygen content: 7%) introduction tube was charged with 60 parts of dehydrated and purified methyl methacrylate and 3 parts of fluorine. 4 parts of boron fluoride ether complex, 50 ° C
Was heated. Next, 140 parts of dehydrated and purified glycidyl methacrylate was added dropwise over 1 hour, and after completion of the addition, the internal temperature was raised to 80 ° C., kept at the same temperature for 6 hours, and cooled to obtain a radically polymerizable resin composition (II). . The reaction was kept in a uniform state throughout, and no production problems such as poor stirring and difficulty in controlling the internal temperature were observed.

The obtained resin composition has a viscosity of 480 at 25 ° C.
It was a pale yellow transparent liquid of cp, the resin solid content was 69% as measured by nonvolatile content, and the residual amount of glycidyl methacrylate was 0.02% as measured by gas chromatography.
The molecular weight of the resin solids measured by gel permeation chromatography is the number average molecular weight (Mn) =
1700, weight average molecular weight (Mw) = 2300. In addition, as a result of NMR analysis of the resin solid, it was confirmed that the obtained polymer had a structure in which an epoxy ring was opened. Comparative Example 1 140 parts of dehydrated and purified n-butyl glycidyl ether and 4 parts of boron trifluoride ether complex were placed in a four-necked flask equipped with a stirring rod, a cooling tube, a dropping funnel, a thermometer, and a dry N ₂ introduction tube. Was mixed at room temperature, and after mixing, the mixture was heated to 50 ° C. while paying attention to heat generation. After reacting at the same temperature for 3 hours, the internal temperature was raised to 80 ° C., and after further reacting at the same temperature for 5 hours, the mixture was cooled to obtain a resin composition. Although the reaction was kept homogeneous throughout the reaction, the viscosity of the product at the end of the reaction increased sharply, resulting in poor stirring, making it difficult to control the internal temperature.

The obtained resin composition has a viscosity at 25 ° C. of 720
The liquid was a yellow viscous liquid of 0 cp, the resin solid content was 99.3% as measured by nonvolatile matter, and the residual butyl glycidyl ether was 0.6% as measured by gas chromatography. The molecular weight of the resin solids measured by gel permeation chromatography is the number average molecular weight (M
n) = 3400 and weight average molecular weight (Mw) = 6900.

An attempt was made to dissolve 70 parts of the obtained yellow viscous liquid in 30 parts of n-butyl glycidyl ether at 50 ° C. However, since a small amount of the gel was contained in the mixture, this was filtered off, and the mixture was filtered at 25 ° C. A yellow transparent liquid having a viscosity of 1230 cp was obtained. Comparative Example 2 A four-necked flask equipped with a stirring rod, a cooling tube, a dropping funnel, a thermometer, and a dry N ₂ introducing tube was charged with 60 parts of dehydrated and purified toluene and 4 parts of a boron trifluoride ether complex, Warmed to ° C. Next, 140 parts of dehydrated and purified glycidyl methacrylate was added dropwise over 1 hour, and after completion of the addition, the internal temperature was raised to 80 ° C., and the temperature was maintained for 6 hours, followed by cooling to obtain a resin composition. The reaction was kept in a uniform state throughout, and no production problems such as poor stirring and difficulty in controlling the internal temperature were observed.

The obtained resin composition was devolatilized at 80 ° C. under a reduced pressure of 20 Torr, and after 6 hours, a pale yellow viscous liquid was obtained. Since the remaining amount of toluene was 2.8% as determined by gas chromatography at this point, the obtained pale yellow viscous liquid was diluted with an equivalent amount of acetone, developed on a stainless steel wide-mouthed tray, and charged at 1 Torr and 80 ° C. Was devolatilized and dried again in a reduced pressure oven to obtain a pale yellow solid.

The amount of the toluene remaining in the obtained pale yellow solid was 0.07% as determined by gas chromatography, and the molecular weight measured by gel permeation chromatography was number average molecular weight (Mn) = 2100, weight average molecular weight ( Mw) = 2900. NMR analysis of the pale yellow solid confirmed that the obtained polymer had a structure in which a methacryloyl group was addition-polymerized.

70 parts of the obtained pale yellow solid was dissolved in 30 parts of methyl methacrylate at 50 ° C.
A light yellow liquid of 0 cp was obtained. [Examples 3 to 19] Radical polymerizable resin compositions (III) to (XI) obtained by reacting according to the methods of Examples 1 and 2 using the raw materials and production conditions shown in Tables 1 and 2
X) The difficulty in controlling the temperature, the presence or absence of poor stirring, and the presence or absence of a gel in the resin composition were evaluated. The results are shown in Tables 1 and 2.

It is apparent from the comparison between the above Examples and Comparative Examples that the intended radically polymerizable resin composition can be advantageously produced by the production method of the present invention.

[0036]

[Table 1]

[0037]

[Table 2]

Examples 20 to 38 Each of the radically polymerizable resin compositions (I) to (XIX) obtained in Examples 1 to 19 was mixed with various polymerization initiators and accelerators, and was cured at room temperature and heated. The curability and photocurability were evaluated. Table 3 shows the results. In addition, the evaluation method about room temperature curability, heat curability, and photocurability is as follows. (Cold at room temperature) To 100 parts of each radical polymerizable resin composition, 0.5 part of a mineral spirits solution of cobalt octylate (metal content 8%) and 1.0 part of methyl ethyl ketone peroxide are added at room temperature and mixed well. Then, the obtained mixture was applied to a thickness of 200 μm on a glass plate using a film applicator. Twenty-four hours later, the state of the coating film was confirmed by finger touch, and was evaluated as ○ when the coating film was cured, and x when the coating film was not cured. (Heat-curing property) To 100 parts of each radically polymerizable resin composition, 1.0 part of benzoyl peroxide was added at room temperature and mixed well, and the resulting mixture was coated on a glass plate with a film applicator to a thickness of 200 μm. Was applied. Next, the glass plate to which the mixture was applied was heated in an oven at 120 ° C. for 30 minutes, then cooled to room temperature, and the state of the coating film was confirmed by finger touch. When the coating film was cured, it was evaluated as ○, and when it was not cured, it was evaluated as ×. (Photocuring) To 100 parts of each radical polymerizable resin composition, 3 parts of Irgacure 651 (photoradical polymerization initiator manufactured by Ciba-Geigy) was added at room temperature and mixed well, and the resulting mixture was mixed with a glass using a bar coater. It was applied on a plate in a thickness of 30 μm. Subsequently, exposure was performed using a conveyor-type ultraviolet irradiation apparatus equipped with one 80 W / cm high-pressure mercury lamp (distance from light source: 10 cm, conveyor speed: 15 m).
/ Min, effective exposure length: 60 cm, ultraviolet irradiation energy amount per pass: 150 mJ / cm ² ). After irradiating ultraviolet light five times, the state of the coating film was confirmed by finger touch.

[0039]

[Table 3]

The chemical formulas of the polymerizable monomer (B), polymerizable monomer (C) and polymerizable monomer (D) used in Examples 1 to 19 are as follows. <Polymerizable monomer (B)> Methyl methacrylate

[0041]

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Butyl acrylate

[0043]

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Dibutyl fumarate

[0045]

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Methacrylamide

[0047]

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[0048] Diethyl maleate

[0049]

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Ethyl methacrylate

[0051]

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N-ethylmaleimide

[0053]

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<Polymerizable monomer (C)> Glycidyl methacrylate

[0055]

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Allyl methacrylate

[0057]

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Tetrahydrofurfuryl acrylate

[0059]

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Dicyclopentenyl acrylate

[0061]

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2-acryloyl-1,3-dioxolan

[0063]

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<Polymerizable monomer (D)> n-butyl glycidyl ether

[0065]

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N-vinylimidazole

[0067]

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N-vinylformamide

[0069]

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Isobutyl vinyl ether

[0071]

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N-vinylpyrrolidone

[0073]

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Α-methylstyrene

[0075]

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Inden

[0077]

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Allylbenzene

[0079]

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Hexyl oxetane

[0081]

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2-methylaziridine

[0083]

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Propylene sulfide

[0085]

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Β-propiolactone

[0087]

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[0088]

According to the present invention, as compared with the conventional method for producing a radically polymerizable resin by bulk polymerization, there is less increase in viscosity and generation of a gel substance, and it is easy to control the temperature of the contents, which is safe. . Further, compared with the conventional solution polymerization, the solvent devolatilization step and the re-dilution step to the polymerizable monomer can be omitted, which is advantageous in all aspects of time, operation and energy.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hirohiro Katsuyama 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 4J011 AA01 AA03 AA05 AC04 BA03 BA04 BB01 BB02 DA02 DA04 FA01 FA07 FB01 FB18 HA03 HB14 HB21 HB22 4J026 AA17 AA31 AA45 AA57 AA59 AA61 AA62 BA27 BA32 BA36 BA38 BB01 DA02 DA19 DB05 DB13 DB19 DB36 GA02 GA06 GA07 4J036 AK08 AK09 AK11

Claims (7)

[Claims] 1. A method for producing a radically polymerizable resin composition comprising a polymer and a radically polymerizable monomer, comprising one reactive group (A) having one cationically polymerizable molecule in one molecule.
The polymerizable monomer (A) having 1) is a liquid polymerizable polymer having at least one reactive group (B1) having substantially radically polymerizable and not cationically polymerizable in one molecule. Cationic polymerization using the monomer (B) as a reaction medium to obtain a radical polymerizable resin composition containing a polymer composed of the polymerizable monomer (A) and the polymerizable monomer (B). A method for producing a radically polymerizable resin composition, which is characterized in that: 2. The polymerizable monomer (A) has one cationically polymerizable reactive group (C1) and at least one radically polymerizable reactive group (C) in one molecule.
2. A polymerizable monomer (C) having the following formula (2):
A method for producing the radically polymerizable resin composition according to the above. 3. Polymerization wherein the polymerizable monomer (A) has one cationically polymerizable reactive group (D1) in one molecule and has no radically polymerizable reactive group. The method for producing a radically polymerizable resin composition according to claim 1, wherein the reactive monomer (D) is used. 4. The polymerizable monomer (A) has one cationically polymerizable reactive group (C1) and at least one radically polymerizable reactive group (C) in one molecule.
2) and a polymerizable monomer (C1) having one cationically polymerizable reactive group (D1) in one molecule and having no radically polymerizable reactive group. The method for producing a radically polymerizable resin composition according to claim 1, wherein the radically polymerizable resin composition is used in combination with a monomer (D). 5. A reactive group having cationic polymerizability (A)
1), (C1) and (D1) are groups having a vinylamino group, a vinylamide group, a styryl group, an allyl group, a vinyl ether group, an epoxy ring, an oxetane ring, a cyclic ether group, an aziridine ring, a cyclic sulfide and a lactone ring. The method for producing a radically polymerizable resin composition according to any one of claims 1 to 4, which is at least one member selected from the group consisting of: 6. The reactive group (B1) having substantially radical polymerizability and not having cationic polymerizability is formed from a (meth) acryloyl group, a (meth) acrylamide group, a maleate group, a fumarate group and a maleimide group. The method for producing a radically polymerizable resin composition according to any one of claims 1 to 5, wherein the method is at least one selected from the group consisting of: 7. A reactive group having radical polymerizability (C)
The radical polymerizable material according to any one of claims 1 to 6, wherein 2) is at least one selected from the group consisting of a (meth) acryloyl group, a (meth) acrylamide group, a maleate group, a fumarate group, and a maleimide group. A method for producing a resin composition.