JP3375872B2 - Method for producing curable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates, in can be suppressed coloration, a method of manufacturing a curable resin composition of the vinyl ester resin can be suitably used for various applications.

[0002]

2. Description of the Related Art Conventionally, it has been known that a curable synthetic resin (hereinafter simply referred to as a resin), when cured, becomes a molded article having excellent corrosion resistance, chemical resistance, water resistance, mechanical properties and the like. Has been. As the resin, a vinyl ester resin,
Urethane (meth) acrylate resin, unsaturated polyester resin, polyester (meth) acrylate resin, etc. are mentioned. The curability is a property of being cured by heating a resin or irradiating an active energy ray. Examples of the photoactive energy rays include light, ultraviolet rays, X-rays, and electron rays.

For example, the above vinyl ester resin is generally produced by reacting an epoxy compound with an unsaturated monobasic acid using an esterification catalyst. However, since a reactive group such as a vinyl group is contained in these resins and their raw materials, the resin is apt to gel due to the bond between the reactive groups during production or storage. Have a point.

It has been known that oxygen is effective as a component for preventing gelation of these resins. For this reason, in the manufacturing process, storage, or transportation, ingenuity in work such as circulating dry air, opening the container at regular intervals, and lowering the filling rate of the resin in the storage container is performed. ing.

However, since a part of such a resin is oxidized by oxygen flowing during the reaction to form a coloring compound, the obtained resin is markedly colored, for example, having a Gardner color number of 3 ~ 8. Moreover, even if a sufficient amount of air is always allowed to coexist, it is difficult to say that the countermeasures against gelation of these resins are sufficient, and there is a very high possibility that gelation will occur during the manufacturing process, storage, or transportation.

Therefore, various other methods have been investigated in order to prevent gelation. For example, JP-A-52-107
Japanese Patent No. 090 discloses a method for stabilizing the storage of a thermosetting resin by adding a living radical compound to the thermosetting resin. The thermosetting resin is obtained by dissolving a reaction product of an epoxy resin and acrylic acid and / or methacrylic acid in a polymerizable unsaturated monomer.

However, in the above publication, the living radical compound used is highly toxic and requires careful handling.

As another method for preventing gelation, storage stability can be obtained by adding a known polymerization inhibitor such as hydroquinone, p-methoxyphenol, t-butylcatechol and phenothiazine to each of the above resins. It is known that the sex improves.

However, in any of the known polymerization inhibitors typified by the above, the obtained curable resin composition is colored depending on whether the polymerization inhibitor itself is colored or aged. That is, when the curable resin composition is continuously exposed to the air, these polymerization inhibitors are oxidized by oxygen dissolved in the curable resin composition and converted into a colored compound, which makes the curable resin composition Color it.

Further, if these polymerization inhibitors are used in combination or added in a large amount in order to further improve the storage stability, the gelling time becomes long when the curable resin composition is cured. There is a tendency that the curability of the resin itself is impaired.

Since these resins are easy to be colored, they are restricted in use even though they have excellent performance.
In the fields of molding materials for P (fiber reinforced plastic), molding materials for casting, lining materials, paints, etc., they are used only for limited applications where appearance is not important. In other words, these resins are, for example, applications such as bathtubs, wash counters, gel coats, etc. where importance is attached to the appearance, and applications where curability by active energy rays, which is excellent as an active energy ray curable resin, is required. Had become unsuitable for.

Therefore, for example, as a method for producing a light-colored vinyl ester resin in which coloring is suppressed, Japanese Patent Publication No.
Japanese Patent Publication No. 34771 discloses a method of reacting an epoxy compound with an unsaturated monobasic acid and an unsaturated polybasic acid using an esterification catalyst in the presence of triphenylstibine in an inert atmosphere.

Further, Japanese Patent Publication No. 6-23232 discloses that
A method of reacting an epoxy compound with an unsaturated monobasic acid and an unsaturated polybasic acid using an esterification catalyst in the presence of phosphorous acid and / or phosphorous acid diester is disclosed.

[0014]

However, when a vinyl ester resin is produced using the above method, or when the above method is applied to the production of urethane (meth) acrylate resin or polyester (meth) acrylate resin, In order to express significant lightness, it is necessary to add a large amount of additives such as the above triphenylstibine, phosphorous acid, phosphite diester, and react in an inert atmosphere or an oxygen-depleted atmosphere. At times, there arises a problem that the raw material and the reaction product are easily gelated.

[0015]

Means for Solving the Problems As a result of intensive studies to avoid the above problems, the present inventors have found that N-oxyls and
For example, vinyl ester resin, urethane (meth) acrylate resin, at least a curable resin composition comprising a type of synthetic resin selected from the group consisting of po Riesuteru (meth) acrylate resin, the physical properties such as storage stability and curability excellent, suppress the coloring with time was thereby leaving have seen that can be suitably used in various applications.

The present invention has been made in view of the above problems, and an object thereof is to have excellent physical properties such as storage stability and curability, and to suppress coloration before and after the start of storage, Thus becomes pale, it is to provide a method for producing a curable resin composition which can be suitably used in various applications.

The method for producing a curable resin composition according to the present invention comprises an epoxy compound, acrylic acid, and methacrylic acid.
Acid, and at least one selected from the group consisting of crotonic acid
Vinyl es obtained by reacting with 1 kind
Tell resin, urethane (meth) acrylate resin, poly
Selected from the group consisting of steal (meth) acrylate resins
The component forming the at least one curable resin is N
-A method of reacting in the presence of oxyls.

[0018] Moreover, in the said manufacturing method, the said N-oxy
General formula (1)

[0019]

[Chemical 2]

(In the formula, X ₁ , X ₂ , and X ₃ are independent of each other.
And represents a hydrogen atom or an —OR ₅ group, and R ₁ , R ₂ , R ₃ ,
R _4's each independently represent an alkyl group having 1 or more carbon atoms.
R ₅ is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.
The amount of the above N-oxyls used is 0.0 based on 100 parts by weight of the resulting curable resin.
It is preferably 0001 parts by weight to 1 part by weight .

Further, N-oxyls which are the same as or different from the N-oxyls used during the production of the curable resin composition may be added after the production of the curable resin composition.

According to the above method, a light-colored curable resin composition can be efficiently stabilized without impairing the excellent physical properties of the curable resin such as corrosion resistance, chemical resistance, water resistance, heat resistance and mechanical properties. Can be manufactured. The above method is suitable as a method for producing a curable resin composition that suppresses coloring without gelation during production.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The following will describe an embodiment of the present invention. In the manufacturing method of the present invention,
In the presence of the above-mentioned N -oxyls , for example vinyl ester
Resin, urethane (meth) acrylate resin, polyester
A small amount selected from the group consisting of
At least one kind of synthetic resin (hereinafter, simply referred to as a resin ) is reacted with a component (raw material) to prepare the above resin, and if necessary, after the preparation, another resin or a reactive monomer, etc. and by further adding, the above-mentioned N- Oki
A curable resin composition containing sils and the above resin can be easily obtained.

The N-oxyls used in the present invention are not particularly limited, and specifically,
For example, 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-
All, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate, 1-oxyl-2, 2,6,6-Tetramethylpiperidin-4-yl-2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-
Ile-stearate, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl-4-t-butylbenzoate, bis (1-oxyl-2,2,6,6-tetramethylpiperidine- 4-yl) succinate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
Bis (1-oxyl-2,2,6,6-tetramethylpiperidine-
4-yl) sebacate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) n-butylmalonic acid ester, bis (1-oxyl-2,2,6,6-tetra Methylpiperidin-4-yl) phthalate, bis (1-oxyl-2,2,6,6-
Tetramethylpiperidin-4-yl) isophthalate, bis (1-oxyl-2,2,6,6-tetramethylpiperidine-4-
Il) terephthalate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N, N'-bis (1-oxyl-2,2,6,6-tetra Methylpiperidin-4-yl) adipamide, N- (1-oxyl-
2,2,6,6-Tetramethylpiperidin-4-yl) caprolactam, N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) dodecylsuccinimide, 2,4,6 -Tris-
[N-butyl-N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)]-s-triazine, 1-oxyl-2,2,6,
6-tetramethylpiperidin-4-one and the like,
It is not particularly limited. Only one type of these N-oxyls may be used, or two or more types may be appropriately mixed and used.

In the present invention, N- which is preferably used
Examples of oxyls include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl. These have low toxicity and are easy to handle, and have excellent storage stability even when added in a small amount.

Further, as the resin used in the present invention, vinyl ester resin, urethane (meth) acrylate resin, it may be at least one resin selected from the group consisting of po Riesuteru (meth) acrylate resins, among them However, vinyl ester resin is most preferable.

[0027] For the vinyl ester resin can be obtained by reacting with an esterification catalyst and d Po <br/> carboxymethyl compound with an unsaturated monobasic acid.

The epoxy compound used as a raw material for the vinyl ester resin is not particularly limited as long as it is a compound having at least one epoxy group in the molecule, and specifically, for example, Epibis type glycidyl ether type epoxy resin obtained by condensation reaction of bisphenols such as bisphenol A and bisphenol S with epihalohydrin; phenol,
Novolak type glycidyl ether type epoxy resin obtained by condensation reaction of novolak, which is a condensate of formalin with cresol and bisphenol, and formalin; condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin Glycidyl ester type epoxy resin obtained by the above; Glycidyl ether type epoxy resin obtained by the condensation reaction of hydrogenated bisphenol or glycols with epihalohydrin; Amine-containing glycidyl ether type epoxy resin obtained by the condensation reaction of hydantoin or cyanuric acid with epihalohydrin Etc. Further, it may be a compound having an epoxy group in the molecule by an addition reaction of these epoxy resins with polybasic acids and / or bisphenols. Only one kind of these epoxy compounds may be used, or two or more kinds thereof may be appropriately mixed and used.

The unsaturated monobasic acid used as the raw material for the vinyl ester resin is not particularly limited, but specific examples thereof include acrylic acid, methacrylic acid and crotonic acid . These unsaturated monobasic acids may be used only one type may be used as a mixture of appropriate two or more.

Specific examples of the esterification catalyst include tertiary amines such as dimethylbenzylamine and tributylamine; quaternary ammonium salts such as trimethylbenzylammonium chloride; lithium chloride, chromium chloride and the like. Inorganic salts; imidazole compounds such as 2-ethyl-4-methylimidazole; tetramethylphosphonium chloride, diethylphenylpropylphosphonium chloride, triethylphenylphosphonium chloride, benzyltriethylphenylphosphonium chloride, dibenzylethylmethyl Phosphonium salts such as phosphonium chloride, benzylmethyldiphenylphosphonium chloride, tetraphenylphosphonium bromide; secondary amines; tetrabutylurea; triphenylphosphine Examples include fins; tritolylphosphine; triphenylstibine, etc., which are not particularly limited, but the use of quaternary ammonium salt, inorganic salt, phosphonium salt, triphenylphosphine, triphenylstibine leads to higher coloring degree. It is more preferable because a smaller resin can be obtained. These esterification catalysts may be used alone or in admixture of two or more.

The urethane (meth) acrylate resin is not particularly limited. For example, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, a hydroxyl group-containing (meth) acrylic compound and It can be obtained by reacting a hydroxyl group-containing allyl ether compound, if necessary.
Further, after reacting the hydroxyl group-containing (meth) acrylic compound with the polyhydroxy compound or the polyhydric alcohol, polyisocyanate may be further reacted.

Specific examples of the polyisocyanate used as the raw material for the urethane (meth) acrylate resin include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and xylyl. Diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate,
Desmodur L (trade name: manufactured by Sumitomo Bayer), Coronate L (trade name: manufactured by Nippon Polyurethane Company), Takenate D102 (trade name: manufactured by Takeda Pharmaceutical Co., Ltd.), Isonate 14
3L (trade name; manufactured by Mitsubishi Kasei Co., Ltd.) and the like, but not particularly limited, are represented by aliphatic diisocyanates represented by hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, and the like. It is more preferable to use an alicyclic diisocyanate, since a resin having a smaller degree of coloring can be obtained. Only one kind of these polyisocyanates may be used, or two or more kinds thereof may be appropriately mixed and used.

Specific examples of the polyhydric alcohols used as the raw material for the urethane (meth) acrylate resin are, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol. , 2-methyl-1,3-propanediol, 1,3-butanediol, adduct of bisphenol A with propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1 , 3-Propanediol, 1,2-Cyclohexane glycol, 1,3-Cyclohexane glycol, 1,4-Cyclohexane glycol, Paraxylene glycol, Bicyclohexyl-4,4'-diol, 2,6-Decalin glycol, 2, 7-decalin glycol Although the like, but is not particularly limited. One type of these polyhydric alcohols may be used, or two or more types may be appropriately mixed and used.

As the polyhydroxy compound used as a raw material for the urethane (meth) acrylate resin,
Examples thereof include polyester polyols and polyether polyols, and specifically, for example, glycerin-
Ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct,
Glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, pentaerythritol-ethylene oxide adduct Substance, pentaerythritol-propylene oxide adduct, pentaerythritol-tetrahydrofuran adduct, pentaerythritol-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran addition , Dipentaerythritol-ethyleneoxy - propylene oxide adduct and the like, but not particularly limited. Only one kind of these polyhydroxy compounds may be used, or two or more kinds thereof may be appropriately mixed and used.

The hydroxyl group-containing (meth) acrylic compound used as a raw material for the urethane (meth) acrylate resin is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester is preferable, and specifically, For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) Di (meth) acrylate of isocyanuric acid,
Examples thereof include pentaerythritol tri (meth) acrylate. Only one kind of these hydroxyl group-containing (meth) acrylic compounds may be used, or two or more kinds thereof may be appropriately mixed and used.

Specific examples of the hydroxyl group-containing allyl ether compound used as a raw material of the above urethane (meth) acrylate resin include, for example, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, and triethylene glycol monoallyl ether. Ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol Monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl Ether, glycerol diallyl ether, although pentaerythritol triallyl ether, and the like, but is not particularly limited. These hydroxyl group-containing allyl ether compounds may be used alone or in a suitable mixture of two or more kinds.

[0037] Also, the polyester (meth) acrylate resin is not particularly limited, for example, can be obtained by reacting an unsaturated or terminated saturated polyester (meth) acrylate compound. As the raw material of the polyester, for example , the same compound as the compound used as the raw material of the unsaturated polyester resin can be used. Of the unsaturated polyester resin
As the dibasic acid used as a raw material, specifically,
For example, maleic acid, maleic anhydride, fumaric acid, ita
Α, β-unsaturated dibasic acids such as conic acid and itaconic anhydride;
Phthalic acid, phthalic anhydride, halogenated phthalic anhydride, a
Sophthalic acid, terephthalic acid, tetrahydrophthalic acid, tephthalic acid
Trahydrophthalic anhydride, hexahydrophthalic acid, hex
Sahydrophthalic anhydride, hexahydroterephthalic acid,
Oxahydroisophthalic acid, succinic acid, malonic acid, gluta
Acid, adipic acid, sebacic acid, 1,10-decanedicarbo
Acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedi
Carboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,3-naphtha
Dicarboxylic acid anhydride, 4,4'-bisphenyldicarbo
Acids and saturated dialkyl esters such as these
Examples thereof include basic acids, but are not particularly limited.
Yes. These dibasic acids may be used alone,
Two or more kinds may be appropriately mixed and used. Above unsaturated
Polyvalent alcohol used as a raw material for polyester resin
Specific examples of such a group include the above-mentioned polyvalent alcohols.
However, it is not particularly limited. This
Only one kind of these polyhydric alcohols may be used
However, two or more kinds may be appropriately mixed and used. Also,
If necessary, dicyclopentadiene compound in the resin skeleton
May be incorporated into.

Specific examples of the (meth) acrylic compound used as a raw material for the polyester (meth) acrylate resin include unsaturated glycidyl compounds,
Examples thereof include unsaturated monobasic acids such as (meth) acrylic acid and glycidyl esters thereof, but are not particularly limited. Only one kind of these (meth) acrylic compounds may be used, or two or more kinds thereof may be appropriately mixed and used.

The mixing conditions and the like of the respective raw materials for obtaining these synthetic resins, that is, the above-mentioned vinyl ester resin, urethane (meth) acrylate resin , and polyester (meth) acrylate resin, are desired. It may be appropriately set depending on the physical properties of the resin to be used and is not particularly limited.

The reactive monomer used as a component of the curable resin may be appropriately selected according to the purpose of use or application and is not particularly limited, but specifically, for example, , Styrene, divinylbenzene, chlorostyrene, (meth) acrylic acid ester, diallyl phthalate, vinyl acetate and the like. Only one kind of these reactive monomers may be used, or two or more kinds thereof may be appropriately mixed and used. Further, only the monofunctional monomer may be used, or the monofunctional monomer and the polyfunctional monomer may be mixed and used. These reactive monomers may be used as a solvent during resin synthesis, or may be used as a solvent for a highly viscous resin for controlling viscosity.

[0041] Also, the curable resin composition may optionally, a polymerization inhibitor other than N- oxyls, curing agent and curing accelerator, rocking change agents, rocking Hensuke agents, solvents, fillers, Includes various additives such as UV absorbers, pigments, thickeners, viscosity reducers, shrinkage reducing agents, defoamers, antioxidants, plasticizers, aggregates, flame retardants, and reinforcing agents as auxiliary materials. You may stay. The amount of these additives used is not particularly limited.

In the present invention, by using the above N-oxyls, the storage stability of the curable resin composition can be greatly improved. When the curable resin composition contains the N-oxyls, it is possible to reduce the amount of oxygen used during production or prevent gelation without using oxygen. Therefore,
According to the present invention, during manufacturing or storage, or during transportation,
It is possible to eliminate the trouble of circulating dry air to prevent gelation and opening the container at regular intervals, and it is possible to improve workability.

The method for producing a curable resin composition according to the present invention comprises the steps of reacting a component forming the curable resin, that is, a raw material of the curable resin in the presence of N-oxyls to obtain the curable resin composition. A method of preparing a composition . The production method of the present invention is applicable to the production of general curable resin compositions, and the curable resin is not particularly limited. Among them, the production method of the present invention, the curable tree
It is particularly preferably used in the production method in which the fat is a kind of curable resin selected from the group consisting of vinyl ester resin, urethane (meth) acrylate resin and polyester (meth) acrylate resin.

The amount of N-oxyls present in the reaction system,
That is, the amount used is not particularly limited, but 0.00001 parts by weight to 100 parts by weight of the obtained curable resin is used.
It is preferably within the range of 1 part by weight, more preferably within the range of 0.001 part by weight to 0.05 part by weight. If the amount of the N-oxyls used is less than 0.00001 parts by weight, the gelation-preventing effect at the time of production cannot be obtained, and there is a risk of production trouble due to gelation, which is not preferable. On the other hand, if the amount of N-oxyls used exceeds 1 part by weight, the curability of the obtained resin may be impaired even if the resin is obtained without gelation during the production, which is not preferable.

The method for allowing the above N-oxyls to coexist in the reaction system is not particularly limited, and for example,
A method of charging a raw material to be a curable resin into a reaction apparatus, heating the mixture to a predetermined temperature with stirring, that is, a reaction temperature, and then supplying N-oxyls, or a method of previously supplying N-oxyl into the raw material of the curable resin. Various methods can be used, such as a method of starting the reaction after supplying and mixing the compounds.

In the present invention, the mixing conditions of each raw material to be the above-mentioned curable resin are not particularly limited, and may be appropriately set according to the desired physical properties of the curable resin. Further, the reaction temperature for carrying out each of the above reactions is not particularly limited, and may be appropriately set so that each reaction can be carried out efficiently. For example, the reaction temperature in the case of reacting an epoxy compound and an unsaturated monobasic acid with an esterification catalyst in the presence of N-oxyls is not particularly limited, but is in the range of 60 ° C to 150 ° C. It is preferable to set within. The reaction time is also not particularly limited, and may be appropriately set so that the reaction is completed depending on the type and combination of raw materials, the amount used, the reaction temperature, and the like. Furthermore, the reaction pressure is not particularly limited, and may be normal pressure (atmospheric pressure), reduced pressure, or increased pressure.

In carrying out each of the above reactions, a polymerization regulator (polymerization inhibitor) different from N-oxyls, a solvent, or a reactive monomer may be used, if necessary. As the polymerization regulator, specifically, for example, hydroquinone,
Examples thereof include methyl hydroquinone, methoxy hydroquinone, t-butyl hydroquinone, benzoquinone, catechol, copper naphthenate, and copper powder, but are not particularly limited. Also, the amount used is not particularly limited. Regarding the addition of the above-mentioned polymerization inhibitor, the addition amount of the polymerization inhibitor is 0.005 parts by weight or less relative to 100 parts by weight of the resin, and it is preferable to add the N-oxyls 0.00001 parts by weight to 1 part by weight in combination with the resin composition. This is more preferable because the change in the degree of coloring with time of the product becomes small.

Each of the above reactions can be carried out without a solvent, but a solvent may be used. The solvent is not particularly limited, and the amount used is also not particularly limited.

The reactive monomer may be appropriately selected according to the purpose of use or application and is not particularly limited. Specific examples include styrene, divinylbenzene and chloro. Examples thereof include styrene, (meth) acrylic acid ester, diallyl phthalate, vinyl acetate and the like. Only one kind of these reactive monomers may be used, or two or more kinds thereof may be appropriately mixed and used. Also,
Only the monofunctional monomer may be used, or the monofunctional monomer and the polyfunctional monomer may be mixed and used. These reactive monomers may be used as a solvent when synthesizing the curable resin,
It may be used as a solvent for a highly viscous curable resin to adjust the viscosity.

[0050]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The degree of coloring, the curing characteristics and the number of storable days of each curable resin composition were measured by the following methods. In addition, "parts" and "%" in the following examples and comparative examples represent "parts by weight" and "% by weight", respectively.

(A) Storable days 600 ml of the resin composition was placed in a screw cap vial having a capacity of 650 ml, and a slight space was left in the vial, and the vial was placed in a constant temperature bath at 60 ° C and 40 ° C. I made them stand upright. After that, about 60 ℃, every 1 day,
At 40 ° C., the resin composition was examined for gelation about every 10 days. For the presence or absence of gelation, invert the vial,
It was examined by observing that when the vial was inverted, the space inside the vial became bubbles and moved upward from the bottom of the vial. The case where the bubbles completely moved from the bottom to the top of the vial was determined as "no gelation", and the case where the bubbles stopped in the middle of the vial was determined as "gelation".

Then, the number of days elapsed from the day when the screw cap vial was placed in a constant temperature bath to the day before the day when the resin composition was first judged to be "gelling" was obtained. did.

(B) Coloring Degree The coloring degree of each curable resin composition was evaluated as Hazen color number. The Hazen color number was measured according to JIS K 6901. First, 2.49 g of potassium chloroplatinate (special grade) and 2.00 g of cobalt chloride (special grade) were dissolved in 200 ml of hydrochloric acid (special grade) and diluted to 2000 ml with distilled water to prepare a standard stock solution. Next, this standard stock solution was added to JIS K 6
They were melted at a ratio specified in 901 to obtain a Hazen color number standard solution.

Then, the Hazen color number standard solution and the curable resin composition were poured into a colorless and transparent flat-bottomed glass tube with an inner diameter of 23 mm and a stopper to a height of 100 mm from the bottom.
It was placed side by side on a white plate and made to stand upright. Then, a flat-bottom glass tube containing this resin composition and a flat-bottom glass tube containing a Hazen color number standard solution were visually compared from above the flat-bottom glass tube under diffused daylight. At this time, the Hazen color number of the curable resin composition was defined as the color number obtained by selecting a Hazen color number standard solution having a concentration most similar to the tested curable resin composition.

In the above-mentioned measurement of the number of days that can be stored at 40 ° C. and 60 ° C., the resin before storage at each temperature is referred to as “resin before storage”, and the “resin before storage” is performed according to the above-mentioned method. The coloring degree of each was investigated.

Further, in the measurement of the number of days that can be stored at each of the above temperatures, when "gelation" is confirmed for the first time,
The resin in the supernatant portion in which the bubbles in the vial move is defined as "resin just before gelation", and according to the above-mentioned method,
The degree of coloring of "resin just before gelation" was examined.

(C) Curing characteristics The curing characteristics of each resin composition are all JIS K 6901.
It was measured according to.

The curing characteristics were measured by the following method.
First, 100 parts of the resin composition and 2 parts of "Percure WO" as a curing agent (manufactured by NOF CORPORATION) were placed in a beaker, and stirred and mixed to obtain a mixture. still,
"Percure WO" is a 50% dilute solution of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexylhexanoate in dioctyl phthalate.

Next, the above mixture was put into a test tube having a diameter of 18 mm so that the depth was 100 mm, and the test tube was held in a thermostatic chamber adjusted to a temperature of 70 ° C. Then, the time taken for the temperature of the mixture to rise from 55 ° C. to 75 ° C. due to the heat of reaction was measured, and this time was taken as the gelation time. The temperature at which the temperature of the mixture reached the maximum was taken as the maximum exothermic temperature, and the time required for the temperature of the mixture to reach the maximum exothermic temperature was taken as the minimum curing time.

[0060] Example 1 a stirrer, a reflux condenser, equipped with a gas inlet tube, and a thermometer
Add a 5 L 4- necked flask to the epoxy flask.
Amount of 465 bisphenol epoxy resin (Tohto Kasei Co., Ltd.
Product name "YD-901"; hereinafter, "YD-901"
And referred) 2500 g, bisphenol type epoxy equivalent of 185
Epoxy resin (manufactured by Tohto Kasei Co., Ltd., trade name "YD-12"
7 "; hereinafter referred to as " YD-127 " ) 580 g, unsaturated
Methacrylic acid 750g, which is a monobasic acid , and esterification
Tetraphenylphosphonium bromide as a catalyst
While charging 11.50 g, 0.04 part of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl which is an N -oxyl is added to 100 parts of the finally obtained vinyl ester resin. It was charged and stirred. Next, while flowing dry nitrogen at 30 ml / min into the above four-necked flask,
After reacting at 115 ℃ for 7 hours, 2100g of styrene monomer
Was added to obtain a vinyl ester resin composition.

The acid value of the vinyl ester resin composition measured by a predetermined method was 5.0 mgKOH / g. The storable days of the obtained vinyl ester resin composition, the curing characteristics, and the coloring degree of the vinyl ester resin composition before storage and immediately before gelation were measured by the above-mentioned method.
The main production conditions of the vinyl ester resin composition and the test results are summarized in Tables 1 and 2.

[0062]

[Table 1]

[0063]

[Table 2]

Example 2 In Example 1 , 4-methoxy-2,2,2,2 was used instead of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl.
Vinyl ester was prepared by the same reaction and operation as in Example 1 , except that 6,6-tetramethylpiperidine-1-oxyl was used in an amount of 0.04 part per 100 parts of the finally obtained vinyl ester resin. A resin composition was obtained.

The acid value of the above vinyl ester resin composition measured by a predetermined method was 5.0 mgKOH / g. The storable days of the obtained vinyl ester resin composition, the curing characteristics, and the coloring degree of the vinyl ester resin composition before storage and immediately before gelation were measured by the above-mentioned method.
Table 1 and Table 2 collectively show the main production conditions of the vinyl ester resin composition and the test results.

[Example 3 ] "YD-901" was placed in the same four-necked flask as in Example 1.
2500 g, "YD-127" 580 g, methacrylic acid 750
g, and tetraphenylphosphonium bromide 1
1.50 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl was added to 0.001 part to 100 parts of the finally obtained vinyl ester resin composition part. It was stirred at. Next, the above four-necked flask was allowed to react at 115 ° C. for 7 hours while flowing dry air at 30 ml / min.

Then, the obtained vinyl ester resin 100
Parts, 2,2-methylene-bis (4-methyl-6-tert-butylphenol) 0.02 parts while adding,
2,2,6,6-Tetramethylpiperidine was added in an amount of 0.005 parts, and 2100 g of styrene monomer was further added to obtain a vinyl ester resin composition. The acid value of the vinyl ester resin composition measured by the predetermined method is 5.0 mgK
It was OH / g.

The shelf life of the obtained vinyl ester resin composition, the curing characteristics, and the degree of coloring of the vinyl ester resin composition before storage and immediately before gelation were measured by the above-mentioned methods. Table 1 and Table 2 collectively show the main production conditions of the vinyl ester resin composition and the test results.

Comparative Example 1 A four-necked flask similar to that used in Example 1 was charged with "YD-901".
2500g, "YD-127" 580g, methacrylic acid 750
g, 2,2-methylene-bis (4-methyl-6) which is a polymerization inhibitor
-tert-butylphenol) 0.600 g, and tetrafe
Charge 11.50 g of Nylphosphonium bromide and stir
did.

Next, dry air was placed in the four-necked flask described above.
After reacting at 115 ° C for 7 hours while flowing at 30 ml / min,
Add 2100 g of styrene monomer as a reactive monomer
Vinyl ester resin (hereinafter, vinyl ester resin
(I)) was obtained.

The shelf life of the obtained vinyl ester resin (I), the curing characteristics, and the coloring degree of the vinyl ester resin composition before storage and immediately before gelation were measured by the above-mentioned method. The main production conditions of the vinyl ester resin (I) and the test results are shown in Tables 1 and 2.

Comparative Example 2 For comparison, 100 parts of a vinyl ester resin (I) obtained by the same method as in Comparative Example 1 was added with 0.05 part of phenothiazine as a conventional polymerization inhibitor for comparison. A vinyl ester resin composition was obtained. The storable days, curing characteristics, and coloring degree of the obtained vinyl ester resin composition for comparison and before storage and immediately before gelation were measured by the above-mentioned method. Table 1 and Table 2 collectively show the main production conditions of the vinyl ester resin composition and the test results.

Comparative Example 3 0.2 part of N-morpholinoacetoacetamide as a conventional polymerization inhibitor was added to 100 parts of vinyl ester resin (I) obtained by the same method as in Comparative Example 1. A vinyl ester resin composition for comparison was obtained by adding. The storable days, curing characteristics, and coloring degree of the obtained vinyl ester resin composition for comparison and before storage and immediately before gelation were measured by the above-mentioned method. Table 1 and Table 2 collectively show the main production conditions of the vinyl ester resin composition and the test results.

It is clear from the results shown in Tables 1 and 2 above.
As described above, the resin composition obtained in this example was obtained in the comparative example.
Storage stability and curing characteristics compared to
Excellent and can suppress coloring over time
I knew that.

Example 4 In a four-necked flask similar to that of Example 1, 1500 g of polyisocyanate hexamethylene diisocyanate, 1400 g of styrene monomer, 2.4 g of dibutyltin dilaurate as a catalyst, and 4-hydroxy-2,2 were used. 240 mg of 6,6,6-tetramethylpiperidine-1-oxyl was charged and stirred.
240 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl correspond to 0.005 parts of the expected yield finally obtained in Example 7.

Next, dry air was added to the four-necked flask described above.
After the temperature was raised to 60 ° C. while flowing at 30 ml / min, 590 g of dipropylene glycol as a polyhydric alcohol was added, and the reaction solution was allowed to react for 3 hours while being kept at 60 ° to 70 ° C.

Thereafter, hydroxypropylmethacrylate 12 which is a hydroxyl group-containing (meth) acrylic compound is further added.
70 g was added and reacted for 5 hours while raising the temperature to 100 ° C. to obtain a urethane (meth) acrylate resin (hereinafter referred to as urethane (meth) acrylate resin (I)).

Further, 4-hydroxy-2,2,6,6- is added to 100 parts of the urethane (meth) acrylate resin (I).
A urethane (meth) acrylate resin composition was obtained by adding 0.02 part of tetramethylpiperidine-1-oxyl. The number of storable days of the obtained urethane (meth) acrylate resin composition, the curing characteristics, and the degree of coloring of the urethane (meth) acrylate resin composition before storage and immediately before gelation were measured by the above-mentioned method. Table 3 summarizes the main production conditions of the urethane (meth) acrylate resin composition and the results of each test.

[0079]

[Table 3]

Example 5 In a four-necked flask similar to that of Example 1, 1650 g of propylene glycol, which is a polyhydric alcohol, 1800 g of isophthalic acid, which is a dibasic acid, and 1720 g of maleic anhydride, were charged and stirred. . Next, an unsaturated polyester was obtained by reacting the above four-necked flask with nitrogen gas at 30 ml / min for 8 hours at 200 ° C. The acid value of the unsaturated polyester measured by a predetermined method was 60 mgKOH / g.

Next, with respect to 100 parts of the unsaturated polyester in the four-neck flask, 0.03 part of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and (meth)
Acrylic compound glycidyl methacrylate 650g
Was added, and the mixture was allowed to react at 140 ° C. for 3 hours while allowing dry air to flow into the four-necked flask at 30 ml / min to obtain a polyester (meth) acrylate resin composition.

The storable days of the obtained polyester (meth) acrylate resin composition, the curing characteristics, and the degree of coloring of the polyester (meth) acrylate resin composition before storage and immediately before gelation were measured by the above-mentioned method. did.
Table 4 shows the main production conditions of the polyester (meth) acrylate resin composition and the results of each test.

[0083]

[Table 4]

[Comparative Example 4 ] A four-necked flask similar to that of Example 1 was charged with the above-mentioned "YD-9".
01 "2500 g, the above-mentioned" YD-127 "580 g, methacrylic acid 480 g, tetraphenylphosphonium bromide 8.90 g, and 4-methoxyphenol 1.20 g as a known polymerization inhibitor were charged, and the same method as in Comparative Example 1 Was used to obtain a vinyl ester resin for comparison. The acid value of the vinyl ester resin for comparison measured by a predetermined method is
It was 5.0 mgKOH / g and Hazen color number was 120.

[Comparative Example 5 ] In Example 1 , except that 1.20 g of hydroquinone as a known polymerization inhibitor was used in place of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl. Is an example
A vinyl ester resin for comparison was obtained by using the same method as in 1 . The acid value of the comparative vinyl ester resin measured by a predetermined method was 5.0 mgKOH / g, and the Hazen color number was 800.

[Comparative Example 6 ] In Example 1 , 11.80 g of 4-methoxyphenol was used in place of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and as a circulating gas. The same reaction and operation as in Example 1 were carried out except that nitrogen gas was used instead of air, and gelation occurred 2 hours after the start of the reaction.

[Comparative Example 7 ] In Example 4 , except that 1.20 g of 4-methoxyphenol was used in place of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl. 4 and obtain a urethane (meth) acrylate resin for comparison using the same method. The resulting urethane (meth) acrylate resin for comparison had a Hazen color number of 200.

Comparative Example 8 Example 4 was repeated except that 100 mg of 4-methoxyphenol was used instead of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl in Example 4. After performing the same reaction and operation as above, hydroxypropyl methacrylate
After 1270 g was added, the mixture was allowed to react for 10 minutes while the temperature was raised to 100 ° C, and gelation occurred.

Comparative Example 9 Hydroquinone 1. was used in place of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl in Example 5 .
Using the same method as in Example 5 except that 20 g was used,
A polyester (meth) acrylate resin for comparison was obtained. The Hazen color number of the obtained polyester (meth) acrylate resin for comparison was 500.

[Comparative Example 10 ] In Example 5 , instead of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, hydroquinone 1
The same reaction and operation as in Example 5 were carried out except that 00 mg was used. After the addition of glycidyl methacrylate, gelation occurred when the reaction was carried out at 140 ° C. for 15 minutes while flowing dry air at 30 ml / min.

As described above, Examples 1 to 5 and Comparative Examples 1 to 10
As is clear from the results described in 1., it was found that the method for producing the resin composition of this example is suitable as a method for producing a curable resin composition in which coloring is suppressed without gelation during production. .

[0092]

As described above, the method for producing a curable resin composition of the present invention impairs the excellent physical properties of the curable resin such as corrosion resistance, chemical resistance, water resistance, heat resistance and mechanical properties. It is possible to efficiently and stably produce a light-colored curable resin composition without producing the effect.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI C08G 63/91 C08G 63/91 // C08K 5/32 C08K 5/32 C08L 63/10 C08L 63/10 67/07 67/07 75/16 75/16 (56) Reference JP-A-9-227642 (JP, A) JP-A-7-271031 (JP, A) JP-A-6-214386 (JP, A) JP-A-6-194837 (JP, A) JP 10-7919 (JP, A) JP 9-143161 (JP, A) JP 64-1764 (JP, A) JP 56-152462 (JP, A) (JP 58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 283/01 C08F 299/00-299/08 C08G 18/67 C08G 59/16 C08G 63/91 C08K 5 / 32 C08L 1/00-101/16

Claims (2)

(57) [Claims] 1. An epoxy compound, acrylic acid, and methacrylic acid.
A small amount selected from the group consisting of phosphoric acid and crotonic acid
Vinyl obtained by reacting at least one kind
From the group consisting of ester resin, urethane (meth) acrylate resin, polyester (meth) acrylate resin
A method for producing a curable resin composition, which comprises reacting at least one selected component forming a curable resin in the presence of N-oxyls. 2. The N-oxyls are represented by the general formula (1) : (In the formula, X ₁ , X ₂ and X ₃ are independently hydrogen atoms.
Child, an —OR ₅ group, and R ₁ , R ₂ , R ₃ , and R ₄ are
Each independently represents an alkyl group having 1 or more carbon atoms, and R ₅ is
Represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms)
And the amount of the above N-oxyls used is 10%
It is 0.00001 weight part-1 weight part with respect to 0 weight part, The manufacturing method of the curable resin composition of Claim 1 characterized by the above-mentioned.