JPH107918A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which is excellent in properties, such as storage stability and curability, and, at the same time, can suppress coloring, derived from a deterioration in resin, with the elapse of time and hence is useful in various application by adding a compd. having a particular structure to a synthetic resin. SOLUTION: This resin compsn. comprises: an N-oxyl compd. having at its molecular end at least one structure selected from among formula I (wherein X1 and X2 represent each H or a -OR5 , -OCOR6 , or -NR7 R8 group; R1 to R4 each independently represents a 1C or higher alkyl group; and R5 to R8 each independently represents a hydrogen atom or a 1-16C alkyl group) and formula II (wherein X3 to X5 represent each H or a -OR13 , -OCOR14 , or -NR15 R16 group; R9 to R12 each independently represents a 1C or higher alkyl group; and R13 to R16 each independently represents a hydrogen atom or a 1-16C alkyl group); and a synthetic resin. Preferred synthetic resins include a vinyl ester resin, a urethane (meth)acrylate resin, and an unsatd. polyester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which can be suitably used for various uses.

[0002]

2. Description of the Related Art Conventionally, vinyl ester resins, urethane (meth) acrylate resins, unsaturated polyester resins,
Synthetic resins such as polyester (meth) acrylate resins and acrylic syrups (hereinafter simply referred to as resins) are known for having excellent corrosion resistance, chemical resistance, water resistance, mechanical properties, and the like.

[0003] For example, the vinyl ester resin is generally produced by reacting an epoxy compound with an unsaturated monobasic acid using an esterification catalyst. However, since these resins and their raw materials contain vinyl groups and the like, they have a problem that they tend to gel during production or storage.

Therefore, various methods have been studied to prevent gelation. Conventionally, oxygen is known to be the most effective component for preventing gelation of these resins. For this reason, in the manufacturing process, during storage, or during transportation, devises are made on the work surface such as circulating dry air, opening the container at regular intervals, and reducing the filling rate of the resin in the storage container. ing.

[0005] However, even if sufficient air is always coexisted, it is hard to say that the countermeasures against gelling of these resins are sufficient, and there is a very high possibility that gelling will occur during the manufacturing process, during storage, or during transportation.

Accordingly, these resins include hydroquinone, p-methoxyphenol, t-butylcatechol,
Storage stability is improved by adding a known polymerization inhibitor such as phenothiazine.

[0007]

However, the known polymerization inhibitors represented by the above all color the resin composition obtained by coloring the polymerization inhibitor itself or by aging. Let it. That is, when the resin composition is continuously exposed to the air, these polymerization inhibitors are oxidized by oxygen dissolved in the resin composition, change into a colored compound, and color the resin composition.

Further, when these polymerization inhibitors are used in combination or added in a large amount in order to further improve the storage stability, the gel time tends to be longer when the resin composition is cured. However, the curability of the resin itself is impaired.

For this reason, these resins are restricted in use while having excellent performance, and are used in the fields of molding materials for FRP (fiber reinforced plastic), molding materials for casting, lining materials, paints and the like. However, it is used only in limited applications where appearance is not important. Therefore, for example, a bathtub, a wash counter, a gel coat, etc., a resin composition which is suitably used for applications where importance is attached to the appearance and applications where excellent photocurability is required as a photocurable resin are desired. ing.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide excellent properties such as storage stability and curability, and to suppress coloring due to deterioration of a resin over time, thereby achieving various purposes. An object of the present invention is to provide a resin composition that can be suitably used for the above-mentioned applications.

[0011]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the inventors of the present invention have found that N-oxyls having a specific structure and vinyl ester resin, urethane (meth) acrylate resin, A resin composition containing a saturated polyester resin, a polyester (meth) acrylate resin, and a synthetic resin such as acrylic syrup has excellent physical properties such as storage stability and curability, and suppresses coloring due to deterioration of the resin over time. As a result, they have found that they can be suitably used for various applications, and have completed the present invention.

That is, the resin composition according to the first aspect of the present invention has the general formula (1)

[0013]

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(Wherein X ₁ and X ₂ are each independently a hydrogen atom, an —OR ₅ group, an —OCOR ₆ group or a —NR ₇ R
Represents _{eight, R 1, R 2, R} 3, R 4 each independently represents an alkyl group having 1 or more carbon atoms, R _5, R _6,
R ₇ and R ₈ are each independently a hydrogen atom or a group having 1 carbon atom.
To 16) and the general formula (2)

[0015]

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(Wherein X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom, an —OR ₁₃ group, an —OCOR ₁₄ group or a —N
Represents R ₁₅ R _{16 group, R 9, R 10, R} 11, R 12 each independently represents a alkyl group having 1 or more carbon atoms, R _13,
R ₁₄ , R ₁₅ , and R ₁₆ each independently represent a hydrogen atom or an alkyl group having 1 to 16 carbon atoms), and an N-oxyl having at least one kind of a structure represented by the following formula: It is characterized by including.

Further, in the resin composition according to the second aspect of the present invention, in the resin composition according to the first aspect, the synthetic resin is a vinyl ester resin, a urethane (meth) acrylate resin, an unsaturated polyester resin, or an unsaturated polyester resin. It is characterized in that it is at least one resin selected from the group consisting of polyester (meth) acrylate resin and acrylic syrup.

Further, the resin composition according to the third aspect of the present invention is the resin composition according to the first or second aspect,
The ratio of N-oxyls to 100 parts by weight of the synthetic resin is 0.00001 to 1 part by weight.

According to the present invention, it is possible to provide a resin composition which is excellent not only in storage stability but also in coloring resistance and curability. Accordingly, the resin composition can be suitably used, for example, in the fields of a molding material for FRP, a molding material for casting, a lining material, a paint, and the like. It can be suitably used for a wide range of applications such as such applications and applications where excellent photocurability is required as a photocurable resin.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below in detail. The resin composition according to the present invention comprises N
-Oxyls and, for example, vinyl ester resins, urethane (meth) acrylate resins, unsaturated polyester resins,
A synthetic resin such as a polyester (meth) acrylate resin and an acrylic syrup (hereinafter, simply referred to as a resin). The resin composition may be prepared by, for example, adding N-oxyls to these resins, or reacting the components (raw materials) to become the above resins in the presence of the N-oxyls, if necessary. Can be easily obtained by mixing other resins or reactive monomers.

The N-oxyls used in the present invention are not particularly limited, but may have the general formula (1)

[0022]

Embedded image

(Wherein X ₁ and X ₂ are each independently a hydrogen atom, an —OR ₅ group, an —OCOR ₆ group or a —NR ₇ R
Represents _{eight, R 1, R 2, R} 3, R 4 each independently represents an alkyl group having 1 or more carbon atoms, R _5, R _6,
R ₇ and R ₈ are each independently a hydrogen atom or a group having 1 carbon atom.
To 16) and the general formula (2)

[0024]

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(Wherein X ₃ , X ₄ and X ₅ are each independently a hydrogen atom, an —OR ₁₃ group, an —OCOR ₁₄ group or a —N
Represents R ₁₅ R _{16 group, R 9, R 10, R} 11, R 12 each independently represents a alkyl group having 1 or more carbon atoms, R _13,
R ₁₄ , R ₁₅ , and R ₁₆ each independently represent a hydrogen atom or an alkyl group having 1 to 16 carbon atoms), and are compounds having at least one type of structure represented by general formula (3)

[0026]

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(Wherein, R ₁₇ and R ₁₈ each independently represent an alkyl group having 4 or more carbon atoms).

Examples of N-oxyls having the above structure include, for example, di-t-butyl nitroxyl,
1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 1-oxyl
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-tetramethylpiperidin-4-yl-stearate, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-
Yl-4-t-butylbenzoate, bis (1-oxyl-2,
2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis (1-oxyl)
-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) n-butylmalonate, bis ( 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis (1 -Oxyl-
2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N, N'-bis (1-oxyl-2,2,6,6-tetramethylpiperidine-4-
Yl) adipamide, N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) caprolactam, N- (1-oxyl-2,2,6,6-tetramethylpiperidine-4- Yl) dodecylsuccinimide, 2,4,6-tris-N-butyl-N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-
Examples thereof include s-triazine, but are not particularly limited. One of these N-oxyls may be used alone, or two or more of them may be used as a mixture.

The resin used in the present invention is not particularly limited, but includes vinyl ester resin, urethane (meth) acrylate resin, unsaturated polyester resin, polyester (meth) acrylate resin, and acrylic syrup. The resin is preferably at least one resin selected from the group consisting of the above, and among them, a vinyl ester resin is most preferable.

The vinyl ester resin is not particularly limited, and can be obtained, for example, by reacting an epoxy compound with an unsaturated monobasic acid using an esterification catalyst.

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. Epibis-type glycidyl ether type epoxy resin obtained by a 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 cresol, bisphenol and formalin with epihalohydrin; glycidyl obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin Ester-type epoxy resins; glycidyl ether-type epoxy resins obtained by condensation reaction of water-added bisphenols and glycols with epihalohydrin; amine-containing glycidyl ether-type epoxy resins obtained by condensation reaction of hydantoin or cyanuric acid with epihalohydrin. . Further, a compound having an epoxy group in a molecule by an addition reaction of these epoxy resins with polybasic acids and / or bisphenols may be used. One of these epoxy compounds may be used alone, or two or more of them may be used as a mixture.

The unsaturated monobasic acid used as a raw material of the vinyl ester resin is not particularly limited, but specific examples include acrylic acid, methacrylic acid, crotonic acid and the like. Further, a half ester such as maleic acid or itaconic acid may be used.
Further, these compounds may be used in combination with polycarboxylic acids such as fumaric acid, itaconic acid and citraconic acid, saturated monocarboxylic acids such as acetic acid, propionic acid, lauric acid and palmitic acid, and saturated polycarboxylic acids such as phthalic acid. An acid or an anhydride thereof, or a compound such as a saturated or unsaturated alkyd having a terminal carboxyl group may be used in combination. One of these unsaturated monobasic acids may be used alone, or two or more of them may be used as a mixture.

Specific examples of the esterification catalyst include tertiary amines such as dimethylbenzylamine and tributylamine; quaternary ammonium salts such as trimethylbenzylammonium chloride; and lithium chloride and chromium chloride. 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, and tetraphenylphosphonium bromide; secondary amines; tetrabutylurea; Fin; Triton reel phosphines; but such triphenylstibine and the like, but is not particularly limited. One of these esterification catalysts may be used, or two or more of them may be used as a mixture.

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 If necessary, it can be obtained by reacting a hydroxyl group-containing allyl ether compound.
Further, after the hydroxyl group-containing (meth) acrylic compound is reacted with the polyhydroxy compound or the polyhydric alcohol, a polyisocyanate may be further reacted.

Examples of the polyisocyanate used as a raw material of the urethane (meth) acrylate resin include, for example, 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene Diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate,
Burnock D-750, Crispon NX (trade name; manufactured by Dainippon Ink and Chemicals, Inc.), Desmodur L (trade name; manufactured by Sumitomo Bayer), Coronate L (trade name; manufactured by Nippon Polyurethane Co., Ltd.), Takenate D102 (trade name) Name;
Takeda Pharmaceutical Co., Ltd.) and Isonate 143L (trade name; manufactured by Mitsubishi Kasei Co., Ltd.), but are not particularly limited thereto. One of these polyisocyanates may be used alone, or two or more of them may be used as a mixture.

Examples of the polyhydric alcohols used as a raw material of the urethane (meth) acrylate resin include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and 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, para-xylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, 2, 7-decalin glycol Although the like, but is not particularly limited. One of these polyhydric alcohols may be used alone, or two or more of them may be used as a mixture.

The polyhydroxy compound used as a raw material of the urethane (meth) acrylate resin includes:
For example, polyester polyols, polyether polyols and the like can be mentioned. 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 addition Product, pentaerythritol-propylene oxide adduct, pentaerythritol-tetrahydrofuran adduct, pentaerythritol-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran addition Substance, dipentaerythritol-ethyleneoxy - propylene oxide adduct and the like, but not particularly limited. One of these polyhydroxy compounds may be used alone, or two or more of them may be used as a mixture.

The hydroxyl group-containing (meth) acrylic compound used as a raw material of the urethane (meth) acrylate resin is not particularly limited, but a hydroxyl group-containing (meth) acrylic ester is preferable. 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,
Pentaerythritol tri (meth) acrylate; One of these hydroxyl group-containing (meth) acrylic compounds may be used alone, or two or more of them may be used as a mixture.

The hydroxyl group-containing allyl ether compound optionally used as a raw material for the urethane (meth) acrylate resin includes, for example, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, 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. One of these hydroxyl group-containing allyl ether compounds may be used alone, or two or more of them may be used as a mixture.

The unsaturated polyester resin is not particularly limited, and can be obtained, for example, by subjecting a dibasic acid and a polyhydric alcohol to a condensation reaction.

Examples of the dibasic acid used as a raw material of the unsaturated polyester resin include, for example, α, β-unsaturated acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride. Dibasic acid; phthalic acid,
Phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid , Glutaric acid, adipic acid, sebacic acid, 1,12-dodecane diacid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,
3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4'-bisphenyldicarboxylic acid, and
Examples thereof include saturated dibasic acids such as dialkyl esters, but are not particularly limited. One of these dibasic acids may be used alone, or two or more of them may be used as a mixture.

Examples of the polyhydric alcohols used as a raw material of the unsaturated polyester resin include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, -Methyl-1,3-propanediol,
1,3-butanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexaneglycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, para-xylene glycol, bicyclohexyl-4,4′-diol, 2,6-decalin glycol, 2,
Examples thereof include 7-decalin glycol, but are not particularly limited. One of these polyhydric alcohols may be used alone, or two or more of them may be used as a mixture. If necessary, a dicyclopentadiene-based compound may be incorporated in the resin skeleton.

The polyester (meth) acrylate resin is not particularly limited, and can be obtained, for example, by reacting a terminal of an unsaturated or saturated polyester with a (meth) acryl compound. As the raw material of the polyester, for example, the same compounds as the compounds exemplified as the raw materials of the unsaturated polyester resin can be used.

As the (meth) acrylic compound used as a raw material of the polyester (meth) acrylate resin, specifically, for example, an unsaturated glycidyl compound,
Examples thereof include, but are not particularly limited to, unsaturated monobasic acids such as (meth) acrylic acid and glycidyl esters thereof. These (meth) acrylic compounds may be used alone or as a mixture of two or more.

The acrylic syrup is not particularly limited. For example, a monomer component (raw material mixture) containing (meth) acrylic acid ester and, if necessary, a vinyl compound is partially polymerized, or It can be obtained by adding a monomer such as a (meth) acrylate or a vinyl compound to a polymer obtained by polymerizing the monomer component. Although a thermoplastic resin can be used as the acrylic syrup, a thermosetting resin is more preferable.

As the above (meth) acrylic acid ester, specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate ) Acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate and the like, but are not particularly limited. One of these (meth) acrylates may be used alone, or two or more of them may be used as a mixture.

As the vinyl compound, specifically,
For example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, vinyl acetate, allyl alcohol,
Examples thereof include ethylene glycol monoallyl ether and propylene glycol monoallyl ether, but are not particularly limited. One of these vinyl compounds may be used alone, or two or more of them may be used as a mixture.

The conditions for mixing these raw materials for obtaining these synthetic resins, ie, the above-mentioned vinyl ester resin, urethane (meth) acrylate resin, unsaturated polyester resin, polyester (meth) acrylate resin, and acrylic syrup, are as follows. What is necessary is just to set suitably according to the physical property etc. of the respectively desired resin, and it does not specifically limit.
In addition, the reaction temperature when performing each of the above reactions is not particularly limited, and may be appropriately set so that each reaction can be performed efficiently. For example, the reaction temperature when a vinyl ester resin is obtained by reacting an epoxy compound with an unsaturated monobasic acid using an esterification catalyst,
Although not particularly limited, it is preferable to set the temperature within the range of 60 ° C to 150 ° C. Also, the reaction time is not particularly limited, and may be appropriately set so that the reaction is completed according to the type and combination of the raw materials, the amount used, the reaction temperature, and the like.

In carrying out each of the above reactions, a polymerization inhibitor may be used, if necessary. As the polymerization inhibitor, specifically, for example, hydroquinone, methylhydroquinone, methoxyhydroquinone, t-butylhydroquinone, benzoquinone, catechol, copper naphthenate,
Although copper powder etc. are mentioned, it is not specifically limited.
The amount of use is not particularly limited.

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 of the solvent is 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 thereof include styrene, divinylbenzene, and chlorobenzene. Examples include styrene, methacrylate, diallyl phthalate, vinyl acetate, and trimethylolpropane triacrylate. One of these reactive monomers may be used alone, or two or more of them may be appropriately used in combination. These reactive monomers may be used as a solvent at the time of resin synthesis, or may be used as a solvent for a high-viscosity resin for adjusting the viscosity.

The method for adding the above-mentioned N-oxyls is not particularly limited. For example, a method for adding after the resin is synthesized, for example, before or after mixing a reactive monomer or another resin, Various methods can be used, such as a method in which N-oxyls are previously mixed in a resin raw material and then polymerized.

In any case, the amount of the N-oxyl is preferably in the range of 0.00001 to 1 part by weight based on 100 parts by weight of the resin.
It is more preferable to add so as to be in the range of 01 parts by weight to 0.05 parts by weight. When the amount of the N-oxyls added is
If the amount is less than 0.00001 part by weight, it is not preferable because effects such as improvement of storage stability and coloring resistance cannot be obtained by adding N-oxyls. On the other hand, if the amount of N-oxyls exceeds 1 part by weight, the curability of the resin may be impaired, which is not preferred.

The resin composition according to the present invention may contain, if necessary, a curing agent, a curing accelerator, a filler, an ultraviolet absorber, a pigment, a thickener, a low-shrinking agent, an antioxidant, and a plasticizer. ,
Various additives such as aggregates, flame retardants, stabilizers, and reinforcing agents may be included. In addition, the usage amount of these additives is not particularly limited.

In the present invention, by using N-oxyls, gelation can be efficiently suppressed, and the storage stability of the resin composition can be greatly improved. When the resin composition contains N-oxyls, for example, the amount of oxygen used in the production can be reduced, and gelation can be prevented without using oxygen. Therefore, according to the present invention, at the time of manufacture, storage, or during transportation, it is possible to circulate dry air to prevent gelation, or to save the trouble of opening the container at regular intervals, Workability can also be improved.

As described above, the resin composition according to the present invention provides an N-oxyl having at least one of the structures represented by the general formulas (1) and (2) at the molecular chain terminal. And synthetic resins. The synthetic resin is preferably at least one resin selected from the group consisting of vinyl ester resins, urethane (meth) acrylate resins, unsaturated polyester resins, polyester (meth) acrylate resins, and acrylic syrups. The ratio of N-oxyls to 100 parts by weight of the synthetic resin is preferably in the range of 0.00001 to 1 part by weight. This makes it possible to provide a resin composition which is excellent not only in storage stability but also in coloring resistance and curability. Therefore, the resin composition, for example,
Molding material for FRP, molding material for casting, lining material,
Along with being suitably used in the field of paints and the like, particularly, bathtubs, wash counters, gel coats, and other applications in which appearance is emphasized, and applications in which excellent photocurability is required as a photocurable resin, It can be suitably used for a wide range of applications.

[0057]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. Incidentally, the coloring degree of each resin composition,
The curing characteristics and the storable days were measured by the following methods. Further, “parts” described in Examples and Comparative Examples indicates “parts by weight”, and “%” indicates “% by weight”.

(A) Color Degree The color degree of each resin composition was evaluated as a Hazen color number, and the Hazen color number was measured according to JIS K6901.
First, 2.49 g of potassium chloroplatinate (special grade) and 2.00 g of cobalt chloride (special grade) were respectively dissolved in 200 ml of hydrochloric acid (special grade), and diluted with distilled water to 2000 ml to prepare a standard stock solution. Next, this standard stock solution was dissolved at a ratio specified in JISK 6901 to obtain a Hazen color number standard solution. Then, the Hazen color number standard solution and the resin composition were poured into a colorless and transparent flat-bottomed glass tube with a stopper with an inner diameter of 23 mm to a height of 100 mm from the bottom, and arranged vertically on a white plate. Next, the concentration (coloring degree) of the Hazen color number standard solution and the resin composition in the flat bottom glass tube was compared with the naked eye from above the flat bottom glass tube under diffused daylight.
Then, the Hazen color number standard solution having the concentration closest to that of the resin composition was selected to obtain the Hazen color number of the resin composition obtained.

(B) Curing Characteristics The curing characteristics of each resin composition are all JIS K690.
It measured according to 1. Curing characteristics when the resin composition was a vinyl ester resin composition were measured by the following method. First, in a beaker, 100 parts of a vinyl ester resin composition and 2 parts of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexylhexanoate as a curing agent (trade name, manufactured by NOF Corporation) Percure WO "), and the mixture was stirred and mixed to obtain a mixture.
Incidentally, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexylhexanoate is a 50% dioctyl phthalate diluted solution.

Next, the above mixture was placed in a test tube having a diameter of 18 mm so as to have a depth of 100 mm, and the test tube was kept in a thermostat controlled at a temperature of 70 ° C. Then, the time required 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 defined as the gel time. The temperature when the temperature of the mixture reached the maximum was defined as the maximum exothermic temperature, and the time from when the temperature of the mixture reached 55 ° C. to the maximum exothermic temperature was defined as the minimum curing time.

The curing properties when the obtained resin composition was an unsaturated polyester resin composition were measured by the following method. First, in a beaker, 100 parts of an unsaturated polyester resin composition, 1.0 part of methyl ethyl ketone peroxide as a curing agent (trade name "Kayamec M", manufactured by Gunzo Akzo Co., Ltd.), 0.5 part of cobalt octenoate as an accelerator, and A mixture was obtained by adding 0.03 parts of N, N-dimethylaniline as a promoting aid, stirring and mixing.

Next, the above mixture was placed in a test tube having a diameter of 18 mm so as to have a depth of 100 mm, and the test tube was kept in a thermostat adjusted to a temperature of 25 ° C. Then, the time required for the temperature of the mixture to rise from 25 ° C. to 30 ° C. due to the heat of reaction was measured, and this time was defined as the gel time. The temperature at which the temperature of the mixture reached the maximum was defined as the maximum exothermic temperature, and the time from when the temperature of the mixture reached 25 ° C. to the maximum exothermic temperature was defined as the minimum curing time.

The curing properties of the urethane (meth) acrylate resin composition and the polyester (meth) acrylate resin composition were measured using the same method as in the case of the vinyl ester resin composition.

(C) Number of storable days The number of storable days of each resin composition was measured by the following method. First, 21 g of the obtained resin composition was placed in a screw-vial bottle having a capacity of 20 ml, and the screw-vial bottle was kept upright in a thermostat at 60 ° C. with some space left inside the screw-vial bottle. Then, every one day, the presence or absence of gelation of the resin composition was examined. The presence or absence of gelation is determined as `` no gelation '' when the air in the space inside the screw-vial vial becomes bubbles and completely moves from the bottom of the screw-vial vial to the top when the screw-vial is inverted. The case where it stopped halfway was defined as "gelation". Then, the elapsed days from the day when the screw-vial bottle was put in the thermostat to the day when the resin composition was first determined to be “gelled” were determined as the number of days that the resin composition can be stored.

Example 1 A 5 L four-necked flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer was prepared.
Bisphenol type epoxy resin having an epoxy equivalent of 465 (trade name “YD-901” manufactured by Toto Kasei Co., Ltd .; hereinafter, “YD-
901 ”) 2500 g, bisphenol-type epoxy resin having an epoxy equivalent of 185 (trade name“ YD-
127 ”; hereinafter, referred to as“ YD-127 ”) 580 g, 750 g of methacrylic acid, which is an unsaturated monobasic acid, and 2,2-methylene-bis (4-methyl-6-tert-butylphenol), which is a bisphenol , Phenols (C))
0.600 g and 11.50 g of tetraphenylphosphonium bromide as an esterification catalyst were charged and stirred. Next, dry air was added to the above four-necked flask at 30 ml / mi.
After reacting at 115 ° C. for 7 hours while flowing with n, 2100 g of a styrene monomer as a reactive monomer was added to obtain a vinyl ester resin (hereinafter referred to as vinyl ester resin (I)). The acid value of the vinyl ester resin (I) measured by a predetermined method was 5.0 mgKOH / g.
Incidentally, 0.600 g of the phenol (C) corresponds to 100 PPm with respect to the vinyl ester resin (I).

Next, 4-hydroxy-2,2,6,6-N-oxyls are added to the vinyl ester resin (I).
A vinyl ester resin composition was obtained by adding 20 ppm of tetramethylpiperidine-1-oxyl (hereinafter referred to as N-oxyls (A)). The storable days and curing properties of the obtained vinyl ester resin composition, and the degree of coloring of the vinyl ester resin composition at the time of preparation and immediately before gelation were measured using the above-described methods. Table 1 summarizes the main production conditions of the vinyl ester resin composition and the results of each test.
Shown in

Example 2 The same reaction and operation as in Example 1 were carried out except that the mixing ratio of N-oxyls (A) to vinyl ester resin (I) was changed from 20 ppm to 100 ppm. Then, a vinyl ester resin composition was obtained. The storable days and curing properties of the obtained vinyl ester resin composition, and the degree of coloring of the vinyl ester resin composition at the time of preparation and immediately before gelation were measured using the above-described methods. Table 1 summarizes main production conditions of the vinyl ester resin composition and test results.

Example 3 In Example 1, N-oxyls (4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl) were used in place of N-oxyls (A). Hereinafter, the same reaction and operation as in Example 1 were carried out except that 20 ppm of N-oxyls (B) was used to obtain a vinyl ester resin composition. The storable days and curing properties of the obtained vinyl ester resin composition, and the degree of coloring of the vinyl ester resin composition at the time of preparation and immediately before gelation were measured using the above-described methods. Table 1 summarizes main production conditions of the vinyl ester resin composition and test results.

Example 4 In the same four-necked flask as in Example 1, 2500 g of “YD-901” and “YD-127” 5
80 g, 750 g of methacrylic acid, and 11.50 g of tetraphenylphosphonium bromide were charged, and N-oxyls (A) were charged at 10 ppm based on the weight of the finally obtained vinyl ester resin, followed by stirring.
Next, the mixture was reacted at 115 ° C. for 7 hours while flowing dry air through the four-necked flask at a flow rate of 30 ml / min, and 2100 g of a 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 and curing properties of the obtained vinyl ester resin composition, and the degree of coloring of the vinyl ester resin composition at the time of preparation and immediately before gelation were measured using the above-described methods. Table 1 summarizes the main production conditions of the vinyl ester resin composition and the results of each test.

Example 5 In Example 4, N-oxyls (B) were used in place of N-oxyls (A) so as to be 10 ppm based on the weight of the finally obtained vinyl ester resin. A vinyl ester resin composition was obtained by performing the same reaction and operation as in Example 4 except for using the same. The acid value of the vinyl ester resin composition measured by a predetermined method is
5.0 mg KOH / g. The storable days and curing properties of the obtained vinyl ester resin composition, and the degree of coloring of the vinyl ester resin composition at the time of preparation and immediately before gelation were measured using the above-described methods. Table 1 summarizes main production conditions of the vinyl ester resin composition and test results.

Example 6 In the same four-necked flask as in Example 1, 2500 g of “YD-901” and “YD-127” 5
80 g, 750 g of methacrylic acid, and 11.50 g of tetraphenylphosphonium bromide were charged, and N-oxyls (A) were charged at 10 ppm based on the weight of the finally obtained vinyl ester resin, followed by stirring.
Next, the mixture was reacted at 115 ° C. for 7 hours while flowing dry air through the four-necked flask at a flow rate of 30 ml / min. Thereafter, phenols (C) were added to the obtained vinyl ester resin in an amount of 200 ppm with respect to the weight thereof, and 2,2,6,6-
Tetramethylpiperidine (hereinafter referred to as amines (D)) was added to a concentration of 50 ppm, and 2100 g of a styrene monomer was further 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 and curing properties of the obtained vinyl ester resin composition, and the degree of coloring of the vinyl ester resin composition at the time of preparation and immediately before gelation were measured using the above-described methods. Table 1 summarizes main production conditions of the vinyl ester resin composition and test results.

[Comparative Example 1] The number of storable days of the vinyl ester resin (I) obtained by using the same method as in Example 1,
The curing properties and the degree of coloring of the vinyl ester resin composition during preparation and immediately before gelation were measured using the methods described above. Table 1 summarizes main production conditions of the vinyl ester resin composition and test results.

Comparative Example 2 Phenothiazine as a conventional polymerization inhibitor (hereinafter referred to as polymerization inhibitor (E)) was applied to vinyl ester resin (I) obtained by the same method as in Example 1. A vinyl ester resin composition for comparison was obtained by adding 500 ppm. The storable days and curing properties of the obtained comparative vinyl ester resin composition, and the degree of coloring of the vinyl ester resin composition at the time of preparation and immediately before gelation were measured using the methods described above. Table 1 summarizes main production conditions of the vinyl ester resin composition and test results.

Comparative Example 3 A vinyl ester resin (I) obtained in the same manner as in Example 1 was used with respect to N-morpholinoacetoacetamide (hereinafter referred to as polymerization inhibition) as a conventional polymerization inhibitor. A vinyl ester resin composition for comparison was obtained by adding 2000 ppm of the agent (F).
The storable days and curing properties of the obtained comparative vinyl ester resin composition, and the degree of coloring of the vinyl ester resin composition at the time of preparation and immediately before gelation were measured using the methods described above. Table 1 summarizes main production conditions of the vinyl ester resin composition and test results.

[0075]

[Table 1]

Example 7 In the same four-necked flask as in Example 1, 1500 g of hexamethylene diisocyanate as a polyisocyanate, 1400 g of styrene monomer, 2.4 g of dibutyltin dilaurate as a catalyst, and N-oxyls (A) 50 mg was charged and stirred. Next, while flowing dry air at a flow rate of 30 ml / min into the four-necked flask, the temperature was raised to 60 ° C.
After raising the temperature to 590 g of dipropylene glycol as polyhydric alcohol was added, and the reaction solution was heated to 60 ° C to 70 ° C.
For 3 hours. Thereafter, 1270 g of hydroxypropyl methacrylate, which is a hydroxyl group-containing (meth) acrylic compound, is further added, and the mixture is reacted for 5 hours while raising the temperature to 100 ° C., to thereby form a urethane (meth) acrylate resin (hereinafter, urethane (meth) acrylate resin (I)). To be described). Furthermore, a urethane (meth) acrylate resin composition was obtained by adding 200 ppm of N-oxyls (A) to the urethane (meth) acrylate resin (I). The storable days and curing characteristics of the obtained urethane (meth) acrylate resin composition, and the degree of coloring of the urethane (meth) acrylate resin composition at the time of preparation and immediately before gelation were measured using the methods described above. Table 2 summarizes the main production conditions of the urethane (meth) acrylate resin composition and the results of each test.

[0077]

[Table 2]

Example 8 A 3 L four-necked flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer was placed
310 g of ethylene glycol, 300 g of diethylene glycol and 320 g of dipropylene glycol as polyhydric alcohols, 700 g of phthalic anhydride and 520 g of maleic anhydride as dibasic acids were charged and stirred. next,
After reacting at 210 ° C. for 7 hours while flowing nitrogen gas into the above four-necked flask at 30 ml / min, styrene monomer 11
By adding 10 g, an unsaturated polyester resin (hereinafter referred to as unsaturated polyester resin (I)) was obtained. The acid value of the unsaturated polyester resin (I) measured by a predetermined method was 43 mgKOH / g.

Next, an unsaturated polyester resin composition was obtained by adding 50 ppm of N-oxyls (A) to the unsaturated polyester resin (I). Storage days of the obtained unsaturated polyester resin composition,
The curing properties and the degree of coloration of the unsaturated polyester resin composition during preparation and immediately before gelation were measured using the methods described above. Table 3 summarizes the main production conditions of the unsaturated polyester resin composition and the results of each test.

Example 9 The same reaction and operation as in Example 1 were performed, except that the mixing ratio of N-oxyls (A) to unsaturated polyester resin (I) was changed from 50 ppm to 200 ppm. To obtain an unsaturated polyester resin composition. The storable days and curing properties of the obtained unsaturated polyester resin composition, and the degree of coloring of the unsaturated polyester resin composition at the time of preparation and immediately before gelation were measured by the above-described methods. Table 3 summarizes the main production conditions of the unsaturated polyester resin composition and the results of each test.

Example 10 The procedure of Example 8 was repeated, except that the N-oxyls (B) were replaced by 200 ppm of N-oxyls (B).
Except for using, the same reaction and operation as in Example 1 were performed to obtain an unsaturated polyester resin composition. The storable days and curing properties of the obtained unsaturated polyester resin composition, and the degree of coloring of the unsaturated polyester resin composition at the time of preparation and immediately before gelation were measured by the above-described methods. Table 3 summarizes the main production conditions of the unsaturated polyester resin composition and the results of each test.

Comparative Example 4 An unsaturated polyester resin for comparison was prepared by adding 50 ppm of a polymerization inhibitor (E) to the unsaturated polyester resin (I) obtained in the same manner as in Example 8. A resin composition was obtained. The storable days and curing properties of the obtained unsaturated polyester resin composition for comparison, and the degree of coloring of the unsaturated polyester resin composition at the time of preparation and immediately before gelation were measured by the above-described methods. Table 3 summarizes the main production conditions of the unsaturated polyester resin composition and the results of each test.

Comparative Example 5 An unsaturated polyester resin (I) obtained by the same method as in Example 1 was treated with 4-tert-butylcatechol (hereinafter referred to as polymerization inhibitor) as a conventional polymerization inhibitor. Agent (H)) By adding 50 ppm, an unsaturated polyester resin composition for comparison was obtained. The storable days and curing properties of the obtained unsaturated polyester resin composition for comparison, and the degree of coloring of the unsaturated polyester resin composition at the time of preparation and immediately before gelation were measured by the above-described methods. Table 3 summarizes the main production conditions of the unsaturated polyester resin composition and the results of each test.

[0084]

[Table 3]

Example 11 The same four-necked flask as in Example 1 was charged with 1650 g of propylene glycol as a polyhydric alcohol, 1800 g of isophthalic acid as a dibasic acid, and 1720 g of maleic anhydride, followed by stirring. . Next, the mixture was reacted at 200 ° C. for 8 hours while flowing dry air at a flow rate of 30 ml / min into the above four-necked flask to obtain an unsaturated polyester. The acid value of the unsaturated polyester measured by a predetermined method was 60 mgKOH / g. Next, N-oxyls (A) were added to the unsaturated polyester in the four-necked flask.
300 ppm and 650 g of glycidyl methacrylate as a (meth) acrylic compound were added and reacted at 140 ° C. for 3 hours while flowing dry air through the four-necked flask at 30 ml / min to obtain a polyester (meth) acrylate resin composition. Was. The storable days and curing properties of the obtained polyester (meth) acrylate resin composition, and the degree of coloring of the polyester (meth) acrylate resin composition at the time of preparation and immediately before gelation were measured using the above-described methods. Table 4 summarizes the main production conditions of the polyester (meth) acrylate resin composition and the results of each test.

Example 12 In the same four-necked flask as in Example 1, 1650 g of propylene glycol and isophthalic acid were added.
1800 g and 1720 g of maleic anhydride were charged and stirred. Next, dry air was added to the above four-necked flask at 30 ml / mi.
The mixture was reacted at 200 ° C. for 8 hours while flowing under the same pressure as above to obtain an unsaturated polyester. The acid value of the unsaturated polyester measured by a predetermined method was 60 mgKOH / g. Next, 100 ppm of phenol (C) and 650 g of glycidyl methacrylate were added to the unsaturated polyester in the four-necked flask.
Was added thereto and reacted at 140 ° C. for 3 hours while flowing dry air through the four-necked flask at a flow rate of 30 ml / min to obtain a polyester (meth) acrylate resin. Next, N-oxyls (A) are added to the polyester (meth) acrylate resin.
By adding 200 ppm, a polyester (meth) acrylate resin composition was obtained. Storage life of the obtained polyester (meth) acrylate resin composition, curing properties, and
The degree of coloration of the polyester (meth) acrylate resin composition at the time of preparation and immediately before gelation was measured using the method described above. Table 4 summarizes the main production conditions of the polyester (meth) acrylate resin composition and the results of each test.

Comparative Example 6 A comparative example was prepared in the same manner as in Example 12, except that 500 ppm of the polymerization inhibitor (E) was used instead of the N-oxyls (A). A polyester (meth) acrylate resin composition was obtained.
The storable days and curing characteristics of the obtained comparative polyester (meth) acrylate resin composition, and the degree of coloring of the polyester (meth) acrylate resin composition at the time of preparation and immediately before gelation were measured using the above-described methods. did. Table 4 summarizes the main production conditions of the polyester (meth) acrylate resin composition and the results of each test.

Comparative Example 7 In Example 12, 480 mg of hydroquinone (hereinafter referred to as polymerization inhibitor (G)) was used in place of phenol (C), and N-oxyl (A) was used in place of phenol (C). A polyester (meth) acrylate resin composition for comparison was obtained in the same manner as in Example 12, except that 200 ppm of the polymerization inhibitor (H) was used. The storable days and curing characteristics of the obtained comparative polyester (meth) acrylate resin composition, and the degree of coloring of the polyester (meth) acrylate resin composition at the time of preparation and immediately before gelation were measured using the above-described methods. did. Table 4 summarizes the main production conditions of the polyester (meth) acrylate resin composition and the results of each test.

[0089]

[Table 4]

As is clear from the results shown in Tables 1 to 4, the resin composition obtained in the present example was compared with the resin composition obtained in the comparative example in storage stability and curing properties. It was found that the coloring was excellent and the coloring over time could be suppressed.

[0091]

As described above, the present invention provides a compound represented by the general formula (1)

[0092]

Embedded image

(Wherein X ₁ and X ₂ are each independently a hydrogen atom, an —OR ₅ group, an —OCOR ₆ group or a —NR ₇ R
Represents _{eight, R 1, R 2, R} 3, R 4 each independently represents an alkyl group having 1 or more carbon atoms, R _5, R _6,
R ₇ and R ₈ are each independently a hydrogen atom or a group having 1 carbon atom.
To 16) and the general formula (2)

[0094]

Embedded image

(Wherein X ₃ , X ₄ and X ₅ are each independently a hydrogen atom, a —OR ₁₃ group, a —OCOR ₁₄ group or a —N
Represents R ₁₅ R _{16 group, R 9, R 10, R} 11, R 12 each independently represents a alkyl group having 1 or more carbon atoms, R _13,
R ₁₄ , R ₁₅ , and R ₁₆ each independently represent a hydrogen atom or an alkyl group having 1 to 16 carbon atoms), and an N-oxyl having at least one kind of a structure represented by the following formula: And a resin composition containing the same.

Further, as described above, the present invention provides at least one of the above synthetic resins selected from the group consisting of vinyl ester resins, urethane (meth) acrylate resins, unsaturated polyester resins, polyester (meth) acrylate resins, and acrylic syrups. The present invention relates to a resin composition which is a kind of resin.

Further, according to the present invention, as described above, the ratio of N-oxyl to 100 parts by weight of the synthetic resin is 0.0
0001 parts by weight to 1 part by weight.

According to the present invention, it is possible to provide a resin composition which is excellent not only in storage stability but also in coloring resistance and curability. Accordingly, the resin composition can be suitably used, for example, in the fields of a molding material for FRP, a molding material for casting, a lining material, a paint, and the like. In addition, such an effect is exhibited that it can be suitably used for a wide range of applications such as such applications and applications in which excellent photocurability is required as a photocurable resin.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 33/06 LHX C08L 33/06 LHX 63/10 63/10 67/06 MSD 67/06 MSD

Claims (3)

[Claims] (1) a compound represented by the general formula (1): (Wherein X ₁ and X ₂ are each independently a hydrogen atom, —O
R ₅ group, —OCOR ₆ group or —NR ₇ R ₈ group,
R ₁ , R ₂ , R ₃ , and R ₄ each independently represent an alkyl group having 1 or more carbon atoms, and R ₅ , R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom or 1 to 16 carbon atoms. And an alkyl group represented by the general formula (2): (Wherein, X ₃ , X ₄ , and X ₅ each independently represent a hydrogen atom, a —OR ₁₃ group, a —OCOR ₁₄ group, or a —NR ₁₅ R ₁₆ group, and R ₉ , R ₁₀ , R ₁₁ , R ₁₂ Each independently represents an alkyl group having 1 or more carbon atoms, and R ₁₃ , R ₁₄ , R ₁₅ , R
₁₆ independently represent a hydrogen atom or an alkyl group having 1 to 16 carbon atoms) N-oxyls having at least one structure among the structures represented by the following formulas and a synthetic resin: Composition. 2. The method according to claim 1, wherein the synthetic resin is at least one resin selected from the group consisting of vinyl ester resins, urethane (meth) acrylate resins, unsaturated polyester resins, polyester (meth) acrylate resins, and acrylic syrups. The resin composition according to claim 1, 3. The resin composition according to claim 1, wherein the ratio of the N-oxyl is 0.00001 to 1 part by weight based on 100 parts by weight of the synthetic resin.