JP2001163935A - Radically polymerizable composition, its manufacturing method and its curing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radically polymerizable composition having an ensured long gelling time and excellent in rapid-drying properties, rapid-curing properties, hardness and other key properties and to provide a preparing method and a curing method thereof. SOLUTION: The radically polymerizable composition comprises a radically polymerizable resin bearing a (meth)acryloyl group, which has ordinary temperature curing characteristics measured according to JIS K 6901 such that a gelling time X <min> and a minimum curing time Y (min) satisfy the requirements; 20<=X<=120 and 0.05<= (Y-X)/X}<=0.6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a radically polymerizable composition, and a method for producing and curing the composition.

[0002]

2. Description of the Related Art Radical polymerizable compositions are used for various molded articles, coating materials, adhesives and the like, because when used, cured products having excellent basic properties such as hardness can be obtained. . Further, it is used as an impregnating agent capable of imparting various characteristics to a material by impregnating and curing various materials. Thus, at present,
Radical polymerizable compositions have become indispensable in producing many industrial products.

[0003] The radically polymerizable composition has a problem in workability so that during the work of molding, coating, impregnation and the like using the same, polymerization does not progress and gelation occurs, and fluidity is not lost. It is necessary to ensure a sufficient gelation time so that no gelation occurs. On the other hand, in order to improve the production efficiency and to suppress the production cost by cycle-up the molding, it is excellent in quick-drying and fast-curing properties so that it is quickly and sufficiently cured after the work is completed. Is desirable.

As a method for adjusting the curing characteristics of the radically polymerizable composition, there is a method for adjusting the amount of the polymerizable unsaturated group, and the like, but it is necessary to ensure a sufficient gelation time and a basic performance such as hardness. It is generally performed by adding a gelling modifier because it is difficult to achieve both. As the gelling modifier, a quinone-based polymerization inhibitor such as hydroquinone is usually used.

However, when the gelling time is extended by using such a gelling agent, the quick-drying property and the quick-curing property are inferior, and the production cost is increased due to a decrease in production efficiency and the like, which causes a problem. In applications where low odor is required to improve the working environment, use high-boiling polymerizable unsaturated monomers instead of low-boiling polymerizable unsaturated monomers such as methyl methacrylate and styrene. Since it is used, a quick-drying effect due to volatilization of the monomer cannot be expected, and the rapid-drying property is particularly reduced. Further, a cured product excellent in basic performance such as hardness cannot be obtained. For this reason, it is necessary to supplement quick-drying and fast-curing properties by increasing the amount of various curing agents and curing accelerators, but the gelation time is shortened, and a sufficient working time cannot be secured.

As described above, since sufficient gelation time is ensured and fast drying property and fast curing property are contradictory curing properties, these conflicting curing properties are compatible with each other, and the hardness is high. It was difficult to obtain a radical polymerizable composition excellent in basic performance such as the above.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, and has a sufficient gelation time and excellent basic properties such as quick-drying / fast-curing properties and hardness. An object of the present invention is to provide a radically polymerizable composition, and a method for producing and curing the composition.

[0008]

The present invention is directed to a radically polymerizable composition containing a radically polymerizable resin having a (meth) acryloyl group, wherein the room temperature curing property measured by JIS K 6901 has a gel time X (minutes) and minimum curing time Y (minutes) are: 20 ≦ X ≦ 120 and 0.05 ≦ ｛(Y−X) /
It is a radically polymerizable composition satisfying the requirement of X｝ ≦ 0.6.

The present invention is a radically polymerizable composition obtained by adding a gelling modifier to a radically polymerizable resin, wherein the gelling modifier contains a saturated organic compound having a primary hydroxyl group. The amount of the gelling modifier is 0.001 to 5 parts by weight based on 100 parts by weight of the radical polymerizable resin.
It is a radical polymerizable composition in parts by weight.

The present invention is a method for producing a radically polymerizable composition, comprising a step of producing a radically polymerizable resin and a step of adding a gelling modifier to the radically polymerizable resin. The agent is a method for producing a radically polymerizable composition containing a saturated organic compound having a primary hydroxyl group.

The present invention relates to a method for curing a radically polymerizable composition in which a gelling regulator, a curing agent and a curing accelerator are added to a radically polymerizable resin to cure the radically polymerizable resin. This is a method for curing a radically polymerizable composition containing a saturated organic compound having a graded hydroxyl group. Hereinafter, the present invention will be described in detail.

The radically polymerizable composition of the present invention contains a radically polymerizable resin having a (meth) acryloyl group. The radical polymerizable resin having a (meth) acryloyl group is a mixture of a radical polymerizable polymer having a (meth) acryloyl group and a polymerizable unsaturated monomer.

In the present invention, the radically polymerizable resin having a (meth) acryloyl group may be a resin having a (meth) acryloyl group and a radically polymerizable group having a substituent bonded to the (meth) acryloyl group. Good. Also,
Instead of the (meth) acryloyl group, a (meth) acryloyl group having a radical polymerizable group having a substituent bonded thereto may be used. Further, it may have a radical polymerizable group other than these groups together with these groups.

The above-mentioned radical polymerizable polymer having a (meth) acryloyl group is not particularly restricted but includes, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate and (meth) acrylate.
It is preferably a macromonomer having an acryloyl group, a thermosetting (meth) acrylic polymer having a (meth) acryloyl group, or the like. These may be used alone or in combination of two or more.

The epoxy (meth) acrylate can be obtained by subjecting a polyfunctional epoxy compound, an unsaturated monobasic acid and, if necessary, an esterification reaction to a polybasic acid. The polyfunctional epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups in a molecule, and examples thereof include a bisphenol type epoxy compound, a hydrogenated bisphenol type epoxy compound, a novolak type epoxy compound, and a hydrogenated novolak type. Epoxy compounds; halogenated epoxy compounds obtained by substituting some of the hydrogen atoms of these epoxy compounds with halogen atoms such as bromine atoms and chlorine atoms. These may be used alone or in combination of two or more.

The bisphenol type epoxy compound is not particularly restricted but includes, for example, a glycidyl ether type epoxy compound obtained by reacting epichlorohydrin or methyl epichlorohydrin with bisphenol A or bisphenol F; epichlorohydrid An epoxy compound obtained by reacting phosphorus or methyl epichlorohydrin with an alkylene oxide adduct of bisphenol A may, for example, be mentioned.

The hydrogenated bisphenol type epoxy compound is not particularly limited. For example, a glycidyl ether type epoxy compound obtained by reacting epichlorohydrin or methyl epichlorohydrin with hydrogenated bisphenol A or hydrogenated bisphenol F is used. Epoxy compound; an epoxy compound obtained by reacting epichlorohydrin or methyl epichlorohydrin with an alkylene oxide adduct of hydrogenated bisphenol A, and the like.

The novolak type epoxy compound is not particularly limited, and examples thereof include an epoxy compound obtained by reacting epichlorohydrin or methyl epichlorohydrin with phenol novolak or cresol novolak. The hydrogenated novolak type epoxy compound is not particularly limited, and examples thereof include an epoxy compound obtained by reacting epichlorohydrin or methyl epichlorohydrin with hydrogenated phenol novolak or hydrogenated cresol novolak.

The average epoxy equivalent of the polyfunctional epoxy compound is not particularly limited.
It is preferred that If it exceeds 900, the handleability of the radically polymerizable composition may decrease due to an increase in the viscosity of the epoxy (meth) acrylate. More preferably, it is 150 to 500.

The unsaturated monobasic acid is not particularly limited as long as it is a monobasic acid having at least one (meth) acryloyl group in the molecule. Examples thereof include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, and the like. Sorbic acid; half esters of unsaturated dibasic acids such as monomethyl maleate, monopropyl maleate and monobutyl maleate. These may be used alone or in combination of two or more. Among these, acrylic acid and methacrylic acid are preferable because they are easily available.

The polybasic acid is not particularly limited as long as it is a dibasic acid having two or more carboxyl groups in the molecule. For example, maleic acid, maleic anhydride, fumaric acid,
Α, β such as itaconic acid, itaconic anhydride and citraconic acid
-Unsaturated dibasic acids and their anhydrides; phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid , Malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, 1,12-dodecane diacid, dimer acid, 2,6-naphthalenedicarboxylic acid,
Saturated dibasic acids such as 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4'-biphenyldicarboxylic acid, and their anhydrides; trimellitic anhydride, etc. Is mentioned. These may be used alone or in combination of two or more.

The ratio between the polyfunctional epoxy compound, the unsaturated monobasic acid and the polybasic acid is not particularly limited, and may be appropriately set according to the basic performance required for the radically polymerizable composition. Good. For example, the ratio of the number of moles of the epoxy group of the polyfunctional epoxy compound to the total number of moles of the carboxyl groups of the unsaturated monobasic acid and the polybasic acid is 1: 1.2 to 1.2: 1. Thus, it is preferable to set the ratio between the two.

The reaction method and reaction conditions in the esterification reaction may be appropriately set according to the basic performance and the like required for the radically polymerizable composition, and are not particularly limited.
For example, it is preferable to set so that the reaction is completed. Further, it is preferable to carry out the reaction in the presence of an esterification catalyst.

The esterification catalyst is not particularly restricted but includes, for example, tertiary amines such as triethylamine, N, N-dimethylbenzylamine and N, N-dimethylaniline; and tertiary amines such as trimethylbenzylammonium chloride and pyridinium chloride. Quaternary ammonium salts; phosphonium compounds such as triphenylphosphine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetrabutylphosphonium bromide; sulfonic acids such as p-toluenesulfonic acid; organic compounds such as zinc octenoate Acid metal salts; inorganic metal compounds, oxo acid metal salts, polyoxo acid metal salts, organic metal compounds, metal complex salts and the like. These may be used alone or in combination of two or more.

In the above esterification reaction, it is preferable to add a polymerization inhibitor or molecular oxygen to the reaction system in order to prevent gelation due to polymerization of a polyfunctional epoxy compound or unsaturated monobasic acid. More preferably, a polymerization inhibitor and molecular oxygen are used in combination.

The polymerization inhibitor is not particularly limited.
For example, hydroquinone, methylhydroquinone, p-
Examples include t-butylcatechol, 2-t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, methoxyhydroquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, and the like. These may be used alone or in combination of two or more.

The molecular oxygen is not particularly limited.
For example, air; a mixed gas of an inert gas such as nitrogen and air or oxygen; These may be used alone or in combination of two or more. When using the above molecular oxygen, molecular oxygen may be blown into the reaction system (so-called bubbling). In order to sufficiently prevent gelation due to polymerization, an antioxidant and molecular oxygen may be used in combination.

The number average molecular weight (Mn) of the epoxy (meth) acrylate is not particularly limited.
It is preferably from 00 to 5000. If it is less than 500, the drying property of the surface during curing of the radically polymerizable composition may decrease. In addition, basic performance such as mechanical strength of the cured product may be reduced. If it exceeds 5,000, the handleability of the radically polymerizable composition may be reduced because the viscosity of the epoxy (meth) acrylate increases. In addition, the radically polymerizable composition may not be fast-drying / fast-curing. In this specification, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC). means.

The urethane (meth) acrylate is, for example, a urethanization reaction of a polyisocyanate compound and a (meth) acrylate compound having a hydroxyl group; a polyisocyanate compound, a polyol compound, and a (meth) acrylate compound having a hydroxyl group And a urethanation reaction between the polyol compound and the unsaturated isocyanate compound.

The above polyisocyanate compound is not particularly restricted but includes, for example, 2,4-tolylene diisocyanate and isomers, hydrides thereof, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate. Trimer, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate and the like. In addition, as commercial products, for example, Millionate MR, Coronate L (both trade names, manufactured by Nippon Polyurethane Industry Co., Ltd.); Burnock D-750, Crisbon NX (both trade names, manufactured by Dainippon Ink and Chemicals, Inc.); L (trade name, manufactured by Sumitomo Bayer); Takenate D102 (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) and the like. These may be used alone,
More than one species may be used in combination. Among these, a diisocyanate compound is preferred.

The above-mentioned (meth) acrylate compound having a hydroxyl group is not particularly limited as long as it is a (meth) acrylate compound having at least one hydroxyl group in a molecule, and examples thereof include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. Hydroxypropyl (meth) acrylate, 3
-Hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like. These may be used alone or in combination of two or more.

The above polyol compound is not particularly restricted but includes, for example, polyether polyols such as polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene glycol, polyoxymethylene glycol; polyester polyols; polybutadiene polyols; alkylenes of bisphenol A Oxides (eg, ethylene oxide, propylene oxide, etc.)
And adducts. These may be used alone,
Two or more kinds may be used in combination.

The number average molecular weight (Mn) of the above polyether polyol is not particularly limited.
Preferably it is 5000. More preferably, 50
0 to 3000. The number average molecular weight (Mn) of the polyester polyol is not particularly limited.
It is preferably from 1,000 to 3,000.

The unsaturated isocyanate compound is not particularly limited as long as it is an isocyanate compound having at least one polymerizable unsaturated bond other than an isocyanate group in a molecule. Examples thereof include methacryloyloxymethyl isocyanate and 2-methacryloyloxyethyl. Isocyanate; an isocyanate compound having a (meth) acryloyl group and an isocyanate group.
These may be used alone or in combination of two or more. The isocyanate compound having a (meth) acryloyl group and an isocyanate group is not particularly limited. For example, a molar ratio of the polyisocyanate compound to the (meth) acrylate compound having a hydroxyl group of 1:
And urethanization reaction can be performed.

The reaction method and reaction conditions in the urethanization reaction may be appropriately set according to the basic performance required for the radically polymerizable composition, and are not particularly limited.
For example, the reaction temperature and the reaction time are preferably set so that the urethanization reaction is completed. Also, for example,
When the polyisocyanate compound, the polyol compound, and the (meth) acrylate compound having a hydroxyl group are subjected to a urethanization reaction, first, the molar ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol compound (isocyanate group) / Hydroxy group) to be 3.0 to 2.0 to form a prepolymer having an isocyanate group at the terminal, and then to have a prepolymer having an isocyanate group and a hydroxyl group. The two groups may be urethanized so that the hydroxyl groups of the (meth) acrylate compound and the hydroxyl groups of the (meth) acrylate compound are substantially equivalent. Further, as mentioned above,
In order to prevent gelation due to polymerization, it is preferable to add a polymerization inhibitor or molecular oxygen to the reaction system.

In the above urethanization reaction, it is preferable to use a urethanization catalyst in order to accelerate the reaction. The urethanization catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine, and general urethanization catalysts such as metal salts such as di-n-butyltin dilaurate. These may be used alone,
Two or more kinds may be used in combination.

The number average molecular weight (Mn) of the urethane (meth) acrylate is not particularly limited.
It is preferably from 00 to 8000. If it is less than 800, the drying property of the surface during curing of the radically polymerizable composition may decrease. In addition, basic performance such as mechanical strength of the cured product may be reduced. If it exceeds 8000, the viscosity of the urethane (meth) acrylate increases, so that the handleability of the radically polymerizable composition may decrease. In addition, the radical polymerizable composition is quick-drying
There is a possibility that it will not be fast-curing. More preferably, 1
000-5000.

The above-mentioned polyester (meth) acrylate can be obtained by subjecting a saturated polyester or unsaturated polyester to an esterification reaction of a compound having a (meth) acryloyl group. The above-mentioned saturated polyester can be obtained by subjecting the above-mentioned dibasic acid containing a saturated dibasic acid and / or their anhydride and a polyhydric alcohol to a condensation reaction. Further, the unsaturated polyester may be the above-mentioned α, β-unsaturated dibasic acid and / or
Alternatively, it can be obtained by a condensation reaction between a dibasic acid containing an anhydride thereof and a polyhydric alcohol.

The polyhydric alcohol is not particularly restricted but includes, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol,
1,3-butanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-
Cyclohexanediol, 1,4-cyclohexanedimethanol, 2-methylpropane-1,3-diol, trimethylolpropane, hydrogenated bisphenol A, alkylene oxide (eg, ethylene oxide, propylene oxide, etc.) adduct of bisphenol A, and the like. . These may be used alone or in combination of two or more.

The reaction method and the reaction conditions in the above condensation reaction may be appropriately set according to the basic performance and the like required for the radically polymerizable composition, and are not particularly limited. It is preferable to set so that the condensation reaction is completed. Further, if necessary, additives such as a catalyst for promoting the condensation reaction and an antifoaming agent can coexist in the reaction system.

The number average molecular weight (Mn) of the saturated polyester and the unsaturated polyester is not particularly limited, and is preferably, for example, 500 to 3000.
When it exceeds 3,000, the handleability of the radically polymerizable composition may be reduced because the viscosity of the polyester (meth) acrylate becomes extremely high.

As the compound having a (meth) acryloyl group, any compound capable of undergoing an esterification reaction with a terminal hydroxyl group or a terminal carboxyl group of a saturated polyester or an unsaturated polyester and having a (meth) acryloyl group can be used. If it is not particularly limited, for example,
The unsaturated monobasic acids described above that react with the terminal hydroxyl group; unsaturated epoxy compounds that react with the terminal carboxyl group, and the like. These may be used alone or in combination of two or more.

The unsaturated epoxy compound is not particularly limited as long as it is a compound having an epoxy group capable of reacting with a carboxyl group and a polymerizable unsaturated bond.
Unsaturated glycidyl ester compounds such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; and mono (meth) acrylates of epoxy resins. These may be used alone or in combination of two or more. Further, an allyl glycidyl ether or the like may be used in combination. The reaction method and reaction conditions in the esterification reaction are the same as in the case of the epoxy (meth) acrylate described above.

In the above esterification reaction, if necessary, a solvent may be used. As the above solvent,
There is no particular limitation as long as it does not inhibit the esterification reaction, and examples thereof include aromatic hydrocarbons such as toluene. These may be used alone or in combination of two or more. In the esterification reaction, since water and alcohol are by-produced, the reaction can be promoted by removing them from the reaction system.

The macromonomer having a (meth) acryloyl group is an oligomer having a polymerizable unsaturated bond at a terminal of a molecular chain, and at least one of the polymerizable unsaturated bonds is a (meth) acryloyl group. . Further, it is preferable that the vinyl polymer has a glass transition temperature (Tg) of 50 ° C. or higher. Further, the polymerizable unsaturated bond may include a styryl group, an aryl group, a vinyl ether group or the like.

The macromonomer having a (meth) acryloyl group is, for example, a polymer having a terminal carboxyl group obtained by radical polymerization of a polymerizable unsaturated monomer in the presence of a chain transfer agent having a carboxyl group (hereinafter referred to as a polymer having a carboxyl group). ,
(Referred to as a carboxyl group-terminated prepolymer) by subjecting a compound having a (meth) acryloyl group such as the above-mentioned unsaturated glycidyl ester compound to an esterification reaction. The chain transfer agent having a carboxyl group is not particularly limited. For example, a thiol compound such as mercaptoacetic acid and 2-mercaptopropionic acid can be used to control the polymerization reaction of a polymerizable unsaturated monomer very easily. Is preferred.

The polymerizable unsaturated monomer is not particularly restricted but includes, for example, (meth) acrylic acid esters; styrene, substituted styrene, aromatic vinyl compounds such as vinyltoluene, divinylbenzene and diallylphthalate; glycidyl ( (Meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, N-vinylpyrrolidone,
Examples include vinyl acetate, vinyl chloride, vinylidene chloride, phenylmaleimide and the like. These may be used alone or in combination of two or more.

The above (meth) acrylic acid ester is not particularly restricted but includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, t-butyl (meth)
(Meth) acrylic acid alkyl esters such as acrylate, 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate; (meth) acrylic acid cycloalkyl esters such as cyclohexyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylamino Basic (meth) acrylates such as ethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and ε-caprolactone ring-opening adduct to 2-hydroxyethyl (meth) acrylate; (Meth) acrylic acid esters having a hydroxyl group such as γ-butyrolactone ring-opening adduct to 2-hydroxyethyl (meth) acrylate; ethylene glycol di (meth) acrylate;
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, etc. No. These may be used alone or in combination of two or more.

Among the above-mentioned polymerizable unsaturated monomers, vinyl acetate,
(Meth) acrylic acid ester having a hydroxyl group,
Use of glycidyl (meth) acrylate or the like may be inappropriate.

The polymerization method of the radical polymerization is not particularly limited, and examples thereof include a solution polymerization method, a bulk polymerization method, and a suspension polymerization method. Among these, the suspension polymerization method is preferred. The polymerization initiator in the radical polymerization is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 4,4-azobis-4-cyanovaleric acid, 1-azobis-1-cyclohexanecarbonitrile And azo compounds such as 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile; benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxide Organic peroxides such as oxyoctoate, t-butylperoxybenzoate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, and the like. These may be used alone or in combination of two or more. Among these, an azo compound is preferable in order to avoid a reaction with a thiol compound or the like as a chain transfer agent.

In the above carboxyl group-terminated prepolymer,
The method for subjecting the compound having a (meth) acryloyl group to an esterification reaction is not particularly limited. For example, a carboxyl group-terminated prepolymer is synthesized by a suspension polymerization method,
It is preferable to carry out the esterification reaction using a polymerizable unsaturated monomer as a solvent. Further, it is preferable that a carboxyl group-terminated prepolymer is synthesized by a suspension polymerization method, and the esterification reaction is performed in a molten state by heating using a kneader or the like.
In any case, the above-mentioned esterification reaction catalyst such as tetrabutylphosphonium bromide may be used.

The number average molecular weight (Mn) of the macromonomer having a (meth) acryloyl group can be determined by appropriately selecting the amounts of a chain transfer agent and a polymerization initiator to be added to the polymerization system. There is no limitation, and for example, it is preferably 1000 to 40000. More preferably, it is 2000-25000.

As the above-mentioned macromonomer having a (meth) acryloyl group, commercially available products, for example, macromonomers AA-6, AA-10, AS-6 and AN-6 (all trade names, manufactured by Toagosei Co., Ltd.) Can be used.
These may be used alone or in combination of two or more.

In the thermosetting (meth) acrylic polymer having a (meth) acryloyl group, at least 50% by weight of the main chain is composed of (meth) acrylate units, and at least one polymerizable non-polymerizable molecule is present in the molecule. A polymer having a saturated bond, wherein at least one of the polymerizable unsaturated bonds is a (meth) acryloyl group. Further, it is preferable that the side chain having a polymerizable unsaturated bond is a polymer bonded to the main chain via an ester bond.

The thermosetting (meth) acrylic polymer can be obtained by subjecting the (meth) acrylic polymer having a carboxyl group and the above-mentioned unsaturated epoxy compound to an esterification reaction. Thus, the epoxy group reacts with the carboxyl group to open the ring, and the side chain having a polymerizable unsaturated bond is bonded to the main chain via an ester bond. Further, it can also be obtained by subjecting a (meth) acrylic polymer having an epoxy group to an esterification reaction with a polymerizable unsaturated monomer having a carboxyl group in the epoxy group. Furthermore, it can also be obtained by adding the above-mentioned unsaturated isocyanate compound to a (meth) acrylic polymer having a hydroxyl group to urethanize the hydroxyl group.

The (meth) acrylic polymer having a carboxyl group can be obtained by polymerizing a monomer component containing the above-mentioned (meth) acrylate and a polymerizable unsaturated monomer having a carboxyl group. be able to.
Among the above-mentioned (meth) acrylates, methyl methacrylate is preferred because the cured product has excellent basic properties such as impact resistance and solvent resistance. Preferably, the main component of the monomer component is methyl methacrylate. As a result, a (meth) acrylic polymer in which the main component of the main chain is a methyl methacrylate unit is obtained, and the basic properties such as weather resistance, transparency, surface gloss, and the appearance and safety are further improved. An improved cured product can be obtained. The content of the (meth) acrylic acid ester in the monomer component is not particularly limited, and is preferably, for example, 50% by weight or more. More preferably, it is 80% by weight or more.

The polymerizable unsaturated monomer having a carboxyl group is not particularly limited as long as it is a polymerizable unsaturated monomer having at least one carboxyl group in the molecule. Examples thereof include acrylic acid, methacrylic acid, Unsaturated monocarboxylic acids such as crotonic acid and vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid; monoesters of these unsaturated dicarboxylic acids; And a saturated monomer. These may be used alone or in combination of two or more.

The unsaturated dicarboxylic acid monoester is not particularly restricted but includes, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, fumarate Monooctyl acid, monoethyl citraconic acid, and the like.

The polymerizable unsaturated monomer having a long-chain carboxyl group is not particularly limited. For example, an acid anhydride obtained by monoesterifying an acid anhydride with a (meth) acrylic acid ester having a hydroxyl group. And the like. The acid anhydride is not particularly limited,
For example, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride and the like can be mentioned. Specific examples of the acid anhydride monoester include succinic acid monoester, phthalic acid monoester, and hexaphthalic acid monoester.

The amount of the polymerizable unsaturated monomer having a carboxyl group to be used is 0.5 to 0.5% based on the total amount of the monomer components.
Preferably it is 20% by weight. If it is less than 0.5% by weight, the cured product may have reduced basic performance such as heat resistance and stain resistance. If it exceeds 20% by weight, the cured product becomes brittle, and basic performance such as impact resistance may be reduced. More preferably, it is 1 to 15% by weight, still more preferably 3 to 10% by weight.

In polymerizing the above monomer component, it is preferable to use the above-mentioned polymerization initiator. In addition, it is preferable to add a chain transfer agent in order to control the polymerization reaction of the monomer component and adjust the weight average molecular weight (Mw) of the thermosetting (meth) acrylic polymer. The chain transfer agent is not particularly limited, and is preferably, for example, a thiol compound because the polymerization reaction of the polymerizable unsaturated monomer can be very easily controlled. Further, α-methylstyrene dimer, carbon tetrachloride and the like can be used. The thiol compound is not particularly limited, and examples thereof include mercaptoacetic acid, 2-mercaptopropionic acid,
-A mercaptan compound having a carboxyl group such as mercaptopropionic acid; a compound having a hydroxyl group such as thioethanol and thiopropanol; an alkyl mercaptan such as t-butyl mercaptan, n-octyl mercaptan and n-dodecyl mercaptan; thiophenol and thionaphthol Thioglycolic acid; octyl thioglycolate, ethylene glycol dithioglycolate, trimethylolpropane tris-
(Thioglycolate), alkyl esters of thioglycolic acid such as pentaerythritol tetrakis- (thioglycolate); β-mercaptopropionic acid; octyl β-mercaptopropionate, 1,4-butanediol di (β-thiopropionate) ), Trimethylolpropane tris- (β-thiopropionate), β-pentaerythritol tetrakis- (β-thiopropionate)
-Alkyl mercaptopropionate and the like. These may be used alone or in combination of two or more.

The amount of the chain transfer agent to be used depends on the desired weight average molecular weight (M) of the thermosetting (meth) acrylic polymer.
What is necessary is just to set suitably according to w), and it does not specifically limit, For example, it is preferable that it is 0.1-15 weight% with respect to the total amount of a monomer component. The amount of the unsaturated epoxy compound to be used may be appropriately set according to the combination with the (meth) acrylic polymer having a carboxyl group, and is not particularly limited. The amount is preferably 0.5 to 2 moles per 1 mole of the polymerizable unsaturated monomer having a carboxyl group used for the production of the polymer. More preferably, 0.8 to
1.5 times mol.

The reaction method and reaction conditions in the above esterification reaction are the same as in the case of the above-mentioned epoxy (meth) acrylate. The esterification catalyst in the esterification reaction is not particularly limited, and examples thereof include phosphonium compounds such as triphenylphosphine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, and tetrabutylphosphonium bromide, and zinc octenoate. Are preferred. The amount of the esterification catalyst used in the esterification reaction may be appropriately set according to the type thereof, the combination with a (meth) acrylic polymer having a carboxyl group, and the like, and is not particularly limited. It is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic polymer having a group. More preferably, 0.1 to 3
Parts by weight. The solvent in the esterification reaction is not particularly limited, and includes, for example, water and an organic solvent. These may be used alone or in combination of two or more.

The weight-average molecular weight (Mw) of the thermosetting (meth) acrylic polymer is 10,000 to 200,000.
It is preferred that If it is less than 10,000, the heat resistance of the cured product may decrease. If it exceeds 200,000, the viscosity of the thermosetting (meth) acrylic polymer becomes too high, and thus the workability of the radical polymerizable composition such as molding may be reduced. Further, when the content is within the above range, the impact resistance of the cured product can be further improved. More preferably, 3000
0 to 150,000, more preferably 40,000
１００100,000.

The thermosetting (meth) acrylic polymer preferably has a double bond equivalent, that is, a molecular weight per polymerizable unsaturated bond of from 500 to 30,000. 5
When it is less than 00, the crosslinked density of the cured product becomes too high, and the cured product may become brittle. for that reason,
The impact resistance of the cured product may be reduced. 30,000
If it exceeds, the crosslinked density of the cured product becomes too low, and the cured product may be inferior in heat resistance. More preferably, it is 2,000 to 10,000, still more preferably, 3
000-7000. When the weight average molecular weight (Mw) of the thermosetting (meth) acrylic polymer is within the above range and the double bond equivalent is within the above range, basic performance such as heat resistance and impact resistance is obtained. Thus, a cured product excellent in the above is obtained.

The polymerizable unsaturated monomer to be mixed with the radically polymerizable resin having a (meth) acryloyl group is not particularly limited, and examples thereof include the same as the above-mentioned polymerizable unsaturated monomer. No. Further, the above-mentioned polymerizable unsaturated monomer having a carboxyl group can also be used. These may be used alone or in combination of two or more. More preferably, it is a polymerizable unsaturated monomer having a (meth) acryloyl group.

The preferred form of the radically polymerizable composition of the present invention is that it exhibits rapid curability and low odor, and is therefore polymerizable unsaturated mixed with the above-mentioned radically polymerizable resin having a (meth) acryloyl group. As the monomer, a compound having a (meth) acryloyl group having a molecular weight of 160 or more is preferable. Among the compounds having a (meth) acryloyl group having a molecular weight of 160 or more, those having a boiling point at 50 mmHg of 90 ° C. or more are preferable. More preferably, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, phenoxyethyl (meth) Acrylate. More preferred are diethylene glycol di (meth) acrylate and methoxydiethylene glycol (meth) acrylate.

The method for mixing the polymerizable unsaturated monomer is not particularly limited, and may be prepared, for example, by mixing the above-mentioned radical polymerizable polymer and the polymerizable unsaturated monomer. Alternatively, a mixture of a radical polymerizable polymer obtained by partially polymerizing a polymerizable unsaturated monomer and an unreacted polymerizable unsaturated monomer may be used.

In the radical polymerizable resin having a (meth) acryloyl group, the weight ratio of the radical polymerizable polymer having a (meth) acryloyl group to the polymerizable unsaturated monomer is not particularly limited. 2: 8-8:
It is preferably 2. When the amount of the polymerizable unsaturated monomer is less than the above range, the viscosity of the radically polymerizable resin becomes too high, so that the workability such as a molding operation of the radically polymerizable composition may be deteriorated. If the amount of the polymerizable unsaturated monomer is larger than the above range, the curability of the radical polymerizable composition may be poor. Further, there is a possibility that the shrinkage of the radical polymerizable composition during curing may increase.
When the radical polymerizable resin having the (meth) acryloyl group is a mixture of a thermosetting (meth) acrylic polymer and a polymerizable unsaturated monomer, more preferably,
3: 7 to 6: 4, more preferably 4: 6 to 5.
5: 4.5. Note that a mixture of a thermosetting (meth) acrylic polymer and a polymerizable unsaturated monomer is also referred to as a thermosetting (meth) acryl syrup.

The radical polymerizable resin having a (meth) acryloyl group may contain a radical polymerizable polymer other than the above-mentioned radical polymerizable polymer having a (meth) acryloyl group. The radical polymerizable compound having a (meth) acryloyl group in the radical polymerizable composition containing the radical polymerizable resin having a (meth) acryloyl group of the present invention (that is, a radical polymerizable polymer and a polymerizable unsaturated monomer) The proportion of the radical polymerizable composition of the present invention is preferably 30 to 100% by weight when the radical polymerizable composition of the present invention is 100 parts by weight. More preferably, it is 40 to 100% by weight. More preferably, 50
１００100% by weight. More preferably, 60 to 100
% By weight. Most preferably, it is 80 to 100% by weight.

In the radical polymerizable composition of the present invention,
Mixing mainly with a compound having a (meth) acryloyl group is a preferred embodiment in view of the fast-curing property and physical properties of the cured product of the present invention. In the practice of the present invention, if the ratio of the compound having a preferred (meth) acryloyl group contained in the radical polymerizable composition of the present invention is adjusted to the above range, the radical polymerizable compound of the other components is As long as it shows radical polymerizability, it may be an unsaturated monomer such as styrene or vinyltoluene, or may be an unsaturated polyester or the like having no (meth) acryloyl group. There is no particular limitation. Radical polymerizable composition of the present invention,
In order to adjust the curability in the radical polymerization, a radical polymerizable resin having a (meth) acryloyl group may be added with a gelling regulator, a curing agent, a curing accelerator, a wax, and the like described below. Good.

According to the radical polymerizable composition of the present invention, a reinforcing material, an auxiliary material (additive) and the like are further added to the radical polymerizable resin having a (meth) acryloyl group in accordance with the basic performance required for the composition. It may be added. The reinforcing material is not particularly limited and includes, for example, glass fiber;
Organic fibers such as polyaramid and polyester; and fibers such as carbon fiber. These fibers can be used in the form of chopped strands, non-woven fabrics and woven fabrics.
The auxiliary material is not particularly limited, for example, an inorganic filler, an organic filler, an ultraviolet absorber, an antioxidant, a plasticizer,
Examples include a leveling agent, an antifoaming agent, an antistatic agent, a flame retardant, a lubricant, a thickener, a low-shrinking agent, a skeleton, and a coloring agent such as a pigment or a dye. The inorganic filler is not particularly limited, for example, aluminum hydroxide, calcium carbonate, clay,
Talc and the like. The amount and method of addition of the gelling agent, curing agent, curing accelerator, waxes, reinforcing material, auxiliary material, and the like are not particularly limited.

In the radical polymerizable composition of the present invention,
Room temperature curing properties as measured by IS K 6901 are:
The gel time X (min) and the minimum curing time Y (min) are: 20 ≦ X ≦ 120 and 0.05 ≦ ｛(Y−X) /
It satisfies the requirement of X｝ ≦ 0.6.

The above-mentioned room temperature curing property means that the resin composition in the radically polymerizable composition is used as a sample in accordance with JIS K690.
Gelation time X measured by the room temperature curing characteristics of X
(Min) and the minimum curing time Y (min). The resin composition means only the radical polymerizable resin when the gelling modifier and waxes described below are not added to the radical polymerizable resin in the radical polymerizable composition. In the radical polymerizable composition, when a gelling regulator and / or wax described later is added to the radical polymerizable resin, the gelling regulator and / or wax are added to the radical polymerizable resin. Means added.

The gel time X (minute) means the time (minute) from the time when the curing agent and the curing accelerator are added to the resin composition to the time when the temperature of the resin composition reaches 30 ° C. I do. The minimum curing time Y (minutes) refers to the time from the time when the curing agent and the curing accelerator are added to the resin composition to the time when the temperature of the resin composition reaches the maximum temperature (the maximum heat generation temperature (° C.)). Means the time (minutes).

The curing agent is a cumene hydroperoxide solution (aromatic hydrocarbon dilution, purity 80%) and te
rt-butyl peroxybenzoate (purity 98%) is used, and as the curing accelerator, cobalt octylate (metal content 8%) and N, N-dimethylaniline are used. In the room temperature curing characteristics, the weight ratio of the resin composition, the curing agent, and the curing accelerator is measured as follows.

Resin composition 100 parts by weight Cobalt octylate (metal content 8%) 0.5 parts by weight N, N-dimethylaniline 0.5 parts by weight Cumene hydroperoxide solution 0.15 parts by weight tert-butyl peroxybenzoate (Purity 98%) 0.5 parts by weight

In the above-mentioned ordinary temperature curing characteristics, if X is less than 20, a sufficient gelling time of the radically polymerizable composition cannot be ensured. If X exceeds 120, the radical polymerizable composition will not be excellent in quick-drying and fast-curing properties. {(YX) / X} is 0.05
When the amount is less than the above, there is a possibility that molding failure or the like may occur in the cured product, and the basic performance of the cured product may be deteriorated.
When {(YX) / X} exceeds 0.6, the radically polymerizable composition may not be excellent in quick-drying and fast-curing properties. Further, as preferred curing characteristics of the present invention,
In consideration of workability and fast-curing properties, the upper limit of X is preferably 60 or less, more preferably 50 or less. Furthermore, 4
0 or less is preferable. On the other hand, as the curing properties of the present invention, the lower limit is that X is 25 or more and Δ (YX) /
X｝ is 0.05 or more and 0.5 or less [more preferably 0.4
5 or less]. On the other hand, X is 30 or more and {(YX) / X} is 0.05 or more and 0.5 or less (preferably 0.45 or less, more preferably 0.4 or less). On the other hand, when X is 33 or more and ｛(YX)
/ X｝ is 0.05 or more and 0.6 or less (preferably 0.5 or less, 0.45 or less, 0.4 or less). That is, the composition of the present invention is, for example, a fast-curing class of 33 ≦ X ≦ 40, but among them, the curing property is relatively long,
Even if it is designed to have curing characteristics within the range that can ensure workability,
The index of quick-curing property represented by (YX) / X is 0.05
A numerical value of not less than 0.6 and not more than 0.6 can be shown.

In the above room temperature curing characteristics, the gel time X
(Min) and the minimum curing time Y (min) are: 25 ≦ X, 30 ≦ Y ≦ 50, and (Y−X) ≦
It is preferable to satisfy the requirements of item 13. More preferably, in the above requirement, (YX) ≦ 11, further preferably (YX) ≦ 10, and most preferably (YX) ≦ 9.

In the above room temperature curing characteristics, the gel time X
Means for ensuring that the (minute) and the minimum curing time Y (minute) satisfy the above requirements are not particularly limited. For example, a radical polymerizable composition described later, and a method for producing and curing the composition may be applied. Is preferred.

The radical polymerizable composition of the present invention is a radical polymerizable composition obtained by adding a gelling modifier to a radical polymerizable resin, wherein the gelling modifier is a saturated organic compound having a primary hydroxyl group. It contains a compound, and the amount of the gelling modifier is 0.001 to 5 parts by weight based on 100 parts by weight of the radical polymerizable resin. The preferred ratio of the saturated organic compound having a primary hydroxyl group contained in the gelling agent is preferably 10 to 100% by weight, based on 100% by weight of the entire gelling agent.
More preferably, it is 30 to 100% by weight, and still more preferably 50 to 100% by weight. The gelling modifier may be diluted with a solvent or the like so that the gelling modifier can be easily added, if necessary, as long as it does not affect the cured form of the radically polymerizable composition of the present invention. The type may be appropriately set if it does not affect the curing.

The above-mentioned gelling modifier is an additive having the function of regulating the curing rate in radical polymerization. In the present invention, it includes a saturated organic compound having a primary hydroxyl group. The saturated organic compound having a primary hydroxyl group is not particularly limited as long as it is an aliphatic saturated organic compound in which a carbon atom having a hydroxyl group has only one carbon group and is aliphatic. Is mentioned. These may be used alone or in combination of two or more.

Methanol, ethanol, propanol,
Butanol, pentanol, propylene glycol, ethylene glycol monomethyl, ethyl ether, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol.

1,3-heptanediol, 1,4-heptanediol, 1,5-heptanediol, 1,6-heptanediol, 1,7-heptanediol, 1,3-heptanediol
Octanediol, 1,4-octanediol, 1,5
-Octanediol, 1,6-octanediol, 1,
7-octanediol, 1,8-octanediol,
1,3-nonanediol, 1,4-nonanediol,
1,5-nonanediol, 1,6-nonanediol,
1,7-nonanediol, 1,8-nonanediol,
1,9-nonanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, triethanolamine.

Among them, the hydroxyl equivalent of the primary hydroxyl group, that is, the molecular weight per one primary hydroxyl group in the compound is preferably 200 g / Eq or less. 2
If it exceeds 00 g / Eq, the effect of adjusting the curability in the radical polymerization of the gelling modifier may be reduced. More preferably, it is 100 g / Eq or less, still more preferably, 50 g / Eq or less. In addition, trimethylolpropane, pentaerythritol, and dipentaerythritol are preferable because the action of the gelling modifier to adjust the curability in radical polymerization is improved.

The above-mentioned gelling modifier may contain the above-mentioned polymerization inhibitor. The method for adding the gelling modifier is not particularly limited. For example, it may be directly added to a radical polymerizable resin and dissolved by performing stirring, heating, or the like, or a suitable solvent, polymerizable unsaturated It may be dissolved in a monomer or the like and then added to the radical polymerizable resin.

The addition amount of the above gelling modifier is 0.001 to 5 parts by weight based on 100 parts by weight of the radical polymerizable resin. If the amount is less than 0.001 part by weight, the effect of adjusting the curability in the radical polymerization of the gelling modifier may be reduced. If the amount exceeds 5 parts by weight, the basic properties such as mechanical strength and water resistance of the cured product may be reduced. More preferably, it is 0.005 to 3 parts by weight, further preferably, 0.01 to 2 parts by weight, further preferably,
0.02 to 2 parts by weight, most preferably 0.03 to 2 parts by weight.
~ 2 parts by weight.

The radical polymerizable composition preferably contains the above-mentioned radical polymerizable resin having a (meth) acryloyl group. Thereby, the action of the gelling modifier is effectively exhibited. The radical polymerizable composition may be obtained by adding a curing agent, a curing accelerator, a wax, a reinforcing material, an auxiliary material (additive), and the like to the radical polymerizable resin as described above. Good. The amount and method of adding these curing agents, curing accelerators, waxes, reinforcing materials, auxiliary materials, and the like are not particularly limited.

The method for producing a radically polymerizable composition of the present invention comprises the steps of producing a radically polymerizable resin and adding a gelling modifier to the radically polymerizable resin. The method is characterized in that the gelling modifier contains a saturated organic compound having a primary hydroxyl group.

The gelling agent is the same as described above. It is also preferable that the amount of addition is the same. The step of producing the radically polymerizable resin is a step of preparing a radically polymerizable resin.

The step of adding a gelling modifier to the radically polymerizable resin may be a step of directly adding a gelling modifier to the radically polymerizable resin and dissolving the mixture by stirring, heating, or the like, or In this step, the modifier is dissolved in an appropriate solvent, a polymerizable unsaturated monomer, or the like, and then added to the radically polymerizable resin.

The radical polymerizable composition preferably contains the above-mentioned radical polymerizable resin having a (meth) acryloyl group. Thereby, the action of the gelling modifier is effectively exhibited. The radical polymerizable composition may be obtained by adding a curing agent, a curing accelerator, a wax, a reinforcing material, an auxiliary material (additive), and the like to the radical polymerizable resin as described above. Good. The amount and method of adding these curing agents, curing accelerators, waxes, reinforcing materials, auxiliary materials, and the like are not particularly limited.

The radically polymerizable composition of the present invention and the radically polymerizable composition produced by the method for producing the radically polymerizable composition of the present invention have a sufficient gelation time, and have a fast drying property and a fast drying property. It has excellent basic properties such as curability and hardness. Therefore, while performing operations such as molding, coating and impregnation using this, sufficient gel time is secured so as not to impair workability, and when the operation is completed, it quickly and sufficiently cures And various molded products,
It can be suitably used as a material such as a coating material or an adhesive or as an impregnating agent.

The method for curing a radically polymerizable composition of the present invention is a method for curing a radically polymerizable composition in which a gelling agent, a curing agent and a curing accelerator are added to a radically polymerizable resin and cured. The gelling modifier contains a saturated organic compound having a primary hydroxyl group.

The gelling agent is the same as described above. It is preferable that the amount and the method of addition be the same. The curing agent is not particularly limited, and includes, for example, diisopropyl peroxydicarbonate, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-
Butyl peroxy-2-ethylhexanoate, 1,
1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butyl hydroperoxide,
Organic peroxides such as t-butyl peroxy neodikenate, t-butyl peroxybenzoate and cumene hydroperoxide; 2,2'-azobisisobutyronitrile, 2,2'-azobisdiethylvaleronitrile and the like And the like. These may be used alone or in combination of two or more.

The amount of the curing agent is not particularly limited. For example, it is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the radical polymerizable resin. 0.1
When the amount is less than part by weight, the amount of radicals generated from the curing agent becomes insufficient, and the radically polymerizable composition may not be cured sufficiently. If it exceeds 10 parts by weight, the radically polymerizable composition may be rapidly cured, and foaming or the like may occur due to decomposition of the curing agent. More preferably, 0.5 to
5 parts by weight.

The curing accelerator has the function of curing the radically polymerizable composition at room temperature or a temperature close thereto, eliminating polymerization inhibition due to oxygen in the air, and eliminating stickiness on the surface of the cured product. Is not particularly limited as long as it is, for example, a polyvalent organic metal salt and / or a polyvalent organic metal complex and, if necessary, an N, N-dialkyl-substituted aromatic amine and / or β-diketone. It is preferable that they include.

The polyvalent organic metal salt and / or the polyvalent organic metal complex generally serves also as a dryer.
The polyvalent organic metal salt is not particularly limited, for example,
Examples thereof include polyvalent metal salts of higher fatty acids such as naphthenic acid, calcium salts of octenoic acid, copper salts, zirconium salts, manganese salts, cobalt salts, lead salts, iron salts, and vanadium salts.
These may be used alone or in combination of two or more. The polyvalent organic metal complex is not particularly limited, and includes, for example, acetylacetonate such as cobalt and manganese. These may be used alone or in combination of two or more.

The N, N-dialkyl-substituted aromatic amine is not particularly restricted but includes, for example, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N- (Dihydroxyethyl)-
p-Toluidine and the like. These may be used alone or in combination of two or more.

The above β-diketones are not particularly restricted but include, for example, methylacetylacetonate, ethylacetylacetonate, propylacetylacetonate and the like. These may be used alone or in combination of two or more.

The amount of the polyvalent organic metal salt and / or polyvalent organic metal complex used in the curing accelerator is not particularly limited. For example, 0.01 to 5 parts by weight based on 100 parts by weight of the radical polymerizable resin. Part. 0.0
If the amount is less than 1 part by weight, the effect of adding the curing accelerator may not be sufficiently exhibited. If the amount exceeds 5 parts by weight, the effect of adding the curing accelerator more than that is not observed. More preferably, it is 0.1 to 3 parts by weight.

The amount of the N, N-dialkyl-substituted aromatic amine and / or β-diketone in the curing accelerator is not particularly limited, and may be, for example, 0.01 to 100 parts by weight of the radical polymerizable resin. It is preferably from 10 to 10 parts by weight. If the amount is less than 0.01 part by weight, the effect of adding the curing accelerator may not be sufficiently exhibited. If the amount exceeds 10 parts by weight, the effect of adding the curing accelerator more than that is recognized. Absent. Further, due to the plasticizing action, the basic performance such as the strength of the cured product may be reduced. More preferably, it is 0.1 to 2 parts by weight.

It is preferable that the addition amount of the above-mentioned curing agent and the above-mentioned curing accelerator is appropriately set within the above-mentioned range depending on the environmental temperature at which the molding operation is performed, the desired operation time, and the like.
The method for adding the curing agent and the curing accelerator is the same as that for the gelling regulator, but when dissolving by heating, at a temperature such that the gelling time of the radically polymerizable composition does not become short. It is preferred to do so.

It is preferable that the radical polymerizable composition is added with a wax having a function of further improving its quick-drying property and quick-curing property. The waxes are not particularly limited, and include, for example, wax (a) containing paraffin wax and / or microcrystalline wax, and / or wax having at least one of a hydroxyl group, a carboxyl group, and an ester bond in a molecule. It is preferable that the composition contains wax (b).

The wax (a) is not particularly limited as long as it is a mixture of hydrocarbons which are solid or semi-solid at room temperature and exist in crude oil. For example, paraffin wax 150, paraffin wax 140, paraffin wax 130, paraffin Paraffin wax such as wax 115 (both trade names, manufactured by Nippon Seiro); Hi-M
Microcrystalline wax such as ic-2065 and Hi-Mic-2045 (both trade names, manufactured by Nippon Seirozu Co., Ltd.) and the like. These may be used alone or in combination of two or more.

The wax (b) is not particularly restricted but includes, for example, fatty acids and fatty acid derivatives having 12 or more carbon atoms such as dodecanoic acid, stearic acid, 12-hydroxystearic acid and octadecyl stearate;
0, alcohols in which ethylene oxide or propylene oxide is added to an alkylphenol or higher alcohol such as Emulmin 200 (both trade names, manufactured by Sanyo Chemical Industries, Ltd.); NPS-9125, NPS-9120,
NPS-6010, HAD-5080, NSP-807
A modified wax derived from a paraffin wax or a microcrystalline wax such as OX-020T, OX-1949 (all trade names, manufactured by Nippon Seiwa Co., Ltd.) by an oxidation reaction or the like; diamond wax (trade name, Shin-Nippon Chemical Co., Ltd.) Derivatives of animal and vegetable fats and oils such as Ceramer 67 and Ceramer 1608 (both trade names, manufactured by Toyo Petrolite Co.)
And the like, and a polymer of an olefin and a carboxyl group-containing monomer. These may be used alone or in combination of two or more.

It is preferable that the wax (b) satisfies at least one of the following requirements (1) to (4). Requirement (1): Acid value is 10 to 300 mgKOH / g, preferably 10 to 200 mgKOH / g, more preferably 1
0-100 mgKOH / g. Requirement (2): hydroxyl value is 10 to 300 mgKOH / g,
It is preferably 10 to 200 mgKOH / g, more preferably 10 to 100 mgKOH / g. Requirement (3): Ester value is 10 to 300 mgKOH /
g, preferably 10 to 200 mgKOH / g, more preferably 10 to 100 mgKOH / g. Requirement (4): The melting point is 50 to 90 ° C.

The above-mentioned acid value is a value in which the amount of potassium hydroxide necessary to neutralize the carboxyl group contained in 1 g of a sample is expressed in mg. The above hydroxyl value is a value in which the amount of potassium hydroxide equivalent to the hydroxyl group contained in 1 g of a sample is expressed in mg. The ester value is a value in which the amount of potassium hydroxide required to saponify the ester bond contained in 1 g of the sample is expressed in mg.

When the wax (b) which satisfies at least one of the requirements (1) to (3) is used together with the wax (a), the radical-polymerizable composition is dried quickly and rapidly. Excellent curability and excellent adhesion can be obtained. More preferably, the wax (b) satisfies at least one of the requirements (1) to (3) and satisfies the requirement (4).

When the wax (a) and the wax (b) are used, the weight ratio of [weight of wax (a)] / [weight of wax (b)] is preferably 1 to 500. If it is less than 1, there is a possibility that the drying property of the radically polymerizable composition may decrease.
The adhesiveness of the radical polymerizable composition may be poor.
More preferably, it is 2 to 300, still more preferably,
2 to 200.

When the wax (a) and the wax (b) are used, the wax (a) and the wax (b)
May be separately added to the radical polymerizable resin and then mixed, or the wax (a) and the wax (b) may be mixed in advance and added to the radical polymerizable resin. The above mixing may be performed at room temperature, or may be performed by heating to about 100 ° C.

The amount of the waxes to be added is not particularly limited. For example, the amount is preferably 0.005 to 2 parts by weight based on 100 parts by weight of the radical polymerizable resin.
If the amount is less than 0.005 parts by weight, the drying property of the radically polymerizable composition may be reduced. If the amount is more than 2 parts by weight, the basic properties such as the strength of the cured product may be reduced. More preferably, it is 0.02 to 0.6 parts by weight.

The radical polymerizable composition preferably contains the above-mentioned radical polymerizable resin having a (meth) acryloyl group. Thereby, the action of the gelling modifier is effectively exhibited. The radical polymerizable composition may be a radical polymerizable resin to which a reinforcing material, an auxiliary material (additive), and the like are added in the same manner as described above. The amount and method of addition of these reinforcing materials and auxiliary materials are not particularly limited. In addition, the radical polymerizable composition of the present invention exhibits good curing characteristics, and thus, for example, the surface hardness of a molded product can reach a predetermined hardness in a relatively short time after the gel starts. . For example, the surface hardness of the molded article can be measured as JIS K 7060 described in Examples as a surface hardness 2 hours after the curing agent is blended. Measured under these conditions, the surface hardness of the cured product after 2 hours of mixing of the curing agent is preferably a cured product of the radically polymerizable composition exhibiting the curing properties of the present invention, and the surface hardness of the cured product is It is preferably 30 or more. It is more preferably 35 or more, and further preferably 40 or more. More preferably, it is 45 or more.

The method for curing the radical polymerizable composition is not particularly limited, and for example, it can be performed by heating. Alternatively, the irradiation can be performed by irradiating active energy rays such as ultraviolet rays, electron beams, and radiations. These methods may be used in combination.

The method for curing a radically polymerizable composition of the present invention ensures a sufficient gelling time of the radically polymerizable composition, improves quick-drying property and quick-curing property, and sets the cured product to a basic property such as hardness. It can be excellent in performance. Therefore, while performing operations such as molding, coating, and impregnation of the radically polymerizable composition, ensure a sufficient gelling time so as not to impair the workability, and quickly and sufficiently cure when the operation is completed. It can be suitably used as a method for curing various molded articles, materials such as coating materials and adhesives, and impregnating agents.

[0116]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Note that “parts” indicates “parts by weight”.

Production Example 1 Epoxy acrylate (a) In a four-necked flask equipped with a thermometer, a stirrer, a gas inlet, and a reflux condenser, 1309 parts of a bisphenol A type epoxy resin (epoxy equivalent: 187), methacrylic acid 60
2 parts, 10 parts of triethylamine and 0.5 part of hydroquinone were charged. This reaction solution is placed in an air stream,
The reaction was performed at 00 ° C. for 4 hours. Furthermore, the acid value is 6 mgKOH
The reaction was aged at 120 ° C. for 3 hours until the pH of the reaction reached / g.
Thereafter, the reaction solution was cooled to 40 ° C., and 479 parts of methyl methacrylate (MMA) was charged and mixed, and the viscosity was 6.5.
Stokes epoxy acrylate (a) was obtained.

Production Example 2 Epoxy acrylate (b) 350 parts of methyl carbitol methacrylate, 205 parts of methacrylic acid, bisphenol A were placed in a four-necked flask equipped with a thermometer, a stirrer, a gas inlet, and a reflux condenser.
445 parts of a type epoxy resin (epoxy equivalent: 187), 6 parts of triethylamine, and 0.1 part of hydroquinone were charged. The reaction solution was heated to 110 ° C. in an air stream, and reacted for 5 hours until the acid value became 5 mgKOH / g.
0.55 parts of tert-butyl catechol was added to obtain an epoxy acrylate (b) having a viscosity of 2.2 Stokes.

Production Example 3 Urethane acrylate (c) Tolylene diisocyanate 696 was placed in a four-necked flask equipped with a thermometer, a stirrer, a gas inlet, and a reflux condenser.
Parts, 212 parts of diethylene glycol, 357 parts of methyl methacrylate, 0.7 part of dibutyltin dilaurate, and
0.3 part of hydroquinone was charged. This reaction solution is
The mixture was heated and stirred at 70 ° C. for 3 hours under an air stream. Thereafter, 520 parts of hydroxyethyl methacrylate was charged into the reaction solution, heated and stirred at 70 ° C. for 2 hours, then heated to 100 ° C., and further heated and stirred for 5 hours to obtain a viscosity of 9.0.
A Stokes urethane acrylate (c) was obtained.

Production Example 4 Polyester acrylate (d) 4 provided with a thermometer, a stirrer, a gas inlet, and a cooling pipe.
In a one-neck flask, 636 parts of diethylene glycol, 444 parts of phthalic anhydride, 516 parts of methacrylic acid, 0.5 part of hydroquinone, and 26 parts of paratoluenesulfonic acid monohydrate were charged. This reaction solution is placed in an air stream for 10 minutes.
The mixture was heated to 0 ° C., and an esterification reaction was performed for 6 hours until the amount of condensed water became 154 parts while removing generated condensed water. Thereafter, the reaction solution was cooled to 40 ° C., and 359 parts of diethylene glycol dimethacrylate was charged and mixed to obtain a polyester acrylate (d) having a viscosity of 1.5 Stokes.

Production Example 5 PMMA macromonomer composition (e) 700 parts of MMA, macromonomer AA-6 (trade name, trade name) in a four-necked flask equipped with a thermometer, a stirrer, a gas inlet, and a reflux condenser. 300 parts of Toagosei Co., Ltd.) and 0.1 part of hydroquinone were charged. This reaction solution was dissolved at 50 ° C. in an air stream to obtain a PMMA macromonomer composition (e) having a viscosity of 1.0 Stokes.

Production Example 6 Thermosetting methacrylic syrup (f) 4 equipped with a thermometer, a stirrer, a gas inlet, and a cooling pipe
In a two-necked flask, 1302 parts of MMA, 98 methacrylic acid
, 2,2'-azobisisobutyronitrile and 56 parts of n-dodecyl mercaptan were charged. This reaction solution was heated and stirred at 80 ° C. for 4 hours under a nitrogen stream to carry out a polymerization reaction. Further, 140 parts of glycidyl methacrylate, 0.4 part of zinc octylate, and 0.14 part of hydroquinone were added to the reaction solution, and the acid value was 10 m.
The mixture was heated and stirred at 100 ° C. under an air stream until gKOH / g was reached. Thereafter, the reaction solution was cooled to 40 ° C,
By mixing 182 parts of MMA, a thermosetting methacryl syrup (f) having a viscosity of 10.0 Stokes was obtained.

Examples 1 to 9 and Comparative Examples 1 to 9 Fourth Embodiment equipped with a thermometer, a stirrer, a gas inlet, and a cooling pipe
In a one-necked flask, 100 parts of the radically polymerizable resin obtained in Production Examples 1 to 6 were charged, and waxes and a gelling agent in the amounts shown in Tables 1 and 2 were added. Stirred for 10 minutes. Then, it cooled to room temperature and obtained the resin composition.

The obtained resin composition was subjected to the above-mentioned J
Room temperature curing properties were measured according to IS K 6901.
In addition, the volatile amount and odor were determined as shown below.Judgment of volatile amount and odor  The amount of monomer volatilization in the resin composition is the amount of weight loss over time
Judgment by the amount of volatilization per unit area calculated from
Presence or absence was determined by human olfaction. That is, 25 ° C atmosphere
Under ambient atmosphere, in a metal cylindrical container with a diameter of 20 cm and a depth of 1 cm
Pour 20 g of the resin composition and measure the amount of weight loss after standing for 30 minutes.
It measured and calculated the amount of volatilization per unit area. Also, the tree
Bring your nose 20cm away from the fat composition and remove the odor
"No" if you don't smell or feel odor, if you feel odor
In this case, it was judged as “present”.

Next, a curing agent and a curing accelerator were added to the obtained resin composition in the same manner as in the measurement of the room temperature curing characteristics to obtain a radically polymerizable composition. 30 g of the obtained radically polymerizable composition was placed in a chopped strand glass mat (450 g / m) having a size of 15 cm × 15 cm.
² ) After impregnating one sheet and forming it on a glass plate in an atmosphere of 25 ° C., 2 hours later, Barcol hardness test according to JIS K 7060 (applicable model: GYZJ 934-1)
Was used to measure the surface hardness. The obtained results are shown in Tables 1 and 2.

[0126]

[Table 1]

In Table 1, paraffin wax 130F is a trade name of paraffin wax manufactured by Nippon Seiro Co., Ltd.
NPS-9125 is a trade name of a modified wax manufactured by Nippon Seiwa. In Comparative Examples 3 and 4, the surface hardness was not measured because the surface after molding was uncured.

[0128]

[Table 2]

In Table 2, in Comparative Example 7, the surface hardness was not measured because the surface after molding was uncured.

[0130]

As described above, the radical polymerizable composition of the present invention has a sufficient gelation time and is excellent in basic properties such as quick-drying property, fast-curing property and hardness since it has the above constitution. is there. Therefore, during the work of molding, coating, impregnation, etc. using this, sufficient gel time is secured so as not to impair the workability, and when the work is completed, it quickly and sufficiently cures It can be suitably used as a material such as various molded articles, coating materials, adhesives, and impregnating agents.

Continued on the front page F term (reference) 4J011 NA19 NB03 NC04 4J027 AA02 AB02 AB03 AB15 AB16 AB17 AB18 AB22 AE02 AE03 AG03 AG04 AG05 AG07 AG23 AG24 AG27 BA04 BA05 BA07 BA09 BA13 BA14 BA15 BA18 CB03 CB04 CD08 CD09

Claims (4)

[Claims] 1. A radical polymerizable composition containing a radical polymerizable resin having a (meth) acryloyl group,
Room temperature curing properties as measured by IS K 6901 are:
The gel time X (min) and the minimum curing time Y (min) are: 20 ≦ X ≦ 120 and 0.05 ≦ ｛(Y−X) /
A radically polymerizable composition, which satisfies the condition of X｝ ≦ 0.6. 2. A radically polymerizable composition obtained by adding a gelling modifier to a radically polymerizable resin, wherein the gelling modifier contains a saturated organic compound having a primary hydroxyl group. The radical polymerizable composition, wherein the amount of the gelling modifier added is 0.001 to 5 parts by weight based on 100 parts by weight of the radical polymerizable resin. 3. A process for producing a radically polymerizable resin,
Adding a gelling modifier to the radically polymerizable resin, wherein the gelling modifier contains a saturated organic compound having a primary hydroxyl group. A method for producing a radically polymerizable composition. 4. A gelling modifier, which is added to a radical polymerizable resin.
A method for curing a radically polymerizable composition in which a curing agent and a curing accelerator are added and cured, wherein the gelling modifier comprises 1
A method for curing a radically polymerizable composition, comprising a saturated organic compound having a graded hydroxyl group.