JP2001011328A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of exhibiting excellent storage stability and further exhibiting good curability at normal temperature without deteriorating curing characteristics when a curing agent is added thereto by making phenylphosphonic acids and an N-oxyl compound exist together in a resin composition. SOLUTION: This composition comprises (A) a radically curable resin (preferably an unsaturated polyester resin, a vinyl ester resin or the like) and (B) a metal compound having redox actions (e.g. a metal salt of an aliphatic carboxylic acid) and consists essentially of (C) phenylphosphonic acids (preferably phenylphosphonic acid, a phenylphosphonic acid ester or the like) and (D) an N-oxyl compound (e.g. 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl). Furthermore, the contents of the components based on the whole resin composition are preferably 10-500 ppm of the component C expressed in terms of weight ratio and preferably 10-1,000 ppm of the component D expressed in terms of the weight ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a curable resin composition and a method for producing the same. More specifically, the present invention relates to a radically curable resin composition having excellent storage stability and capable of exhibiting good curability at room temperature, and a method for producing the same.

[0002]

2. Description of the Related Art Radical curable resins represented by unsaturated polyester resins, vinyl ester resins, urethane (meth) acrylate resins, unsaturated polyester (meth) acrylate resins, etc. are relatively easy to handle because they are liquid. In addition, since it is a typical thermosetting resin that cures quickly and gives molded products having excellent properties such as mechanical strength and water resistance, it has been used in the field of paints and adhesives or fiber reinforced plastic (FRP). Widely used for material applications. In particular, large molded products such as septic tanks and boats, paints,
For applications such as adhesives, radical curable resins that can be cured at room temperature are desired.

In order to cure a radical-curable resin at room temperature, a curing agent such as an organic peroxide and a metal compound having a redox effect, for example, are mixed with the resin at room temperature to generate radicals. A method of initiating curing is employed. When the resin is actually cured at room temperature by this method, the resin and a metal compound having a redox effect are stored in advance in a mixed state in consideration of the complexity of the operation and the like, and immediately before the curing. It is common to add a curing agent to the mixture and provide it for molding or the like.

However, when a resin and a metal compound are mixed in advance, gelation is likely to occur during storage, and in order to maintain storage stability for a long period of time, the resin and the metal compound are generally mixed. A polymerization inhibitor is added to the resin composition. Since this polymerization inhibitor prevents the curing of the resin, when a sufficient amount of the polymerization inhibitor is used to obtain satisfactory storage stability, the curing characteristics of the resin itself are reduced, and the Unless the amount of the agent added is increased, there is a problem that curing becomes difficult.

When a radical-curable resin is used for molding or the like, it is necessary to perform an operation of pouring or applying the resin into a molding die after the curing agent is added and before curing starts. Because of this, a certain pot life,
That is, it is necessary to adjust the addition amount of the curing agent according to the outside air temperature at that time in order to secure a time until the gelation starts and the molding operation becomes difficult. In particular, when the outside temperature is high, the amount of the hardening agent usually has to be reduced in order to secure the pot life, but when the amount of the hardening agent is small as described above, the hardening after gelation is performed. The reactivity of the reaction is significantly reduced.

For example, as a conventional polymerization inhibitor, a quinone-based polymerization inhibitor is widely used, but when it is added to a radical-curable resin composition, a sufficient effect is obtained with an addition amount within a range capable of maintaining curing characteristics. And storage stability cannot be improved. Further, as a polymerization inhibitor having improved polymerization inhibition effect, for example, phenothiazine and the like are known,
Even when this is added to the radical curable resin composition,
Although the storage stability is improved, it is not sufficient, and there is a disadvantage that the curing characteristics of the resin itself are reduced and the curing is significantly delayed.

As described above, it has been difficult for the conventional curable resin composition to obtain good storage stability while maintaining curing characteristics.

[0008]

Accordingly, an object of the present invention is to provide a curable resin composition having excellent storage stability and exhibiting good curability at room temperature without deteriorating the curing properties. It is in.

[0009]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems. As a result, by having both the phenylphosphonic acids and the N-oxyl compound coexist in the resin composition, the resin composition has excellent storage stability, and at the room temperature without impairing the curing properties when the curing agent is added. It was found that a resin composition exhibiting good curability and suitable for room temperature curing was obtained, and the present invention was completed.

That is, the curable resin composition according to the present invention is a curable resin composition comprising a radical curable resin and a metal compound having a redox effect, and comprises a phenylphosphonic acid, N-oxyl And a compound as an essential component.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below in detail. In the present invention, the radical-curable resin refers to a resin that is cured by a radical polymerization reaction. As the radical curable resin, specifically, for example, unsaturated polyester resin, vinyl ester resin (epoxy (meth) acrylate resin), urethane (meth) acrylate resin, unsaturated polyester (meth) acrylate resin and the like are preferably used. Can be These exemplary resins are:
Each of them may be used alone or two or more of them may be used in combination. And these radical curable resins are usually
Unsaturated polyester, epoxy (meth) acrylate,
It contains a resin solid consisting of a polymer such as urethane (meth) acrylate or unsaturated polyester (meth) acrylate and an appropriate amount of a polymerizable monomer.

The unsaturated polyester of the present invention is obtained by subjecting an acid component essentially comprising an unsaturated polybasic acid and a component comprising a polyhydric alcohol and / or an epoxy compound (hereinafter referred to as an alcohol component) to condensation polymerization. Polymer. The acid component may further contain a saturated polybasic acid such as an aromatic saturated polybasic acid or an aliphatic saturated polybasic acid, if necessary. Further, a monovalent acid may be used instead of a part of the polybasic acid. Further, a monohydric alcohol may be used instead of a part of the polyhydric alcohol.

Although the acid value of the unsaturated polyester is not particularly limited, it is generally preferable that the acid value is 40 or less. The molecular weight of the unsaturated polyester is not particularly limited, but preferably has a number average molecular weight in the range of 500 to 20,000. The unsaturated polybasic acid used for the acid component is a polymerizable unsaturated unsaturated compound having two or more substituents capable of forming an ester bond by reacting with a hydroxyl group or an epoxy group contained in the alcohol component. Any compound having a bond may be used. Specific examples of the unsaturated polybasic acid include α, β-unsaturated polybasic acids such as maleic acid, fumaric acid, aconitic acid, and itaconic acid, and β, γ-unsaturated polybasic acids such as dihydromuconic acid. Acid or
Examples include anhydrides of these acids, halides of these acids, and alkyl esters of these acids. These exemplified compounds may be used alone or in combination of two or more.

The saturated polybasic acid optionally used for the acid component includes malonic acid, succinic acid, methylsuccinic acid,
2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid Aliphatic saturated polybasic acids such as 3,3,3-diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc. And saturated alicyclic saturated polybasic acids such as hetonic acid, 1,2-hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid, and trans-1,4-cyclohexanedicarboxylic acid; Acid anhydrides, halides of these acids, and alkyl ester derivatives of these acids. These exemplified compounds may be used alone or in combination of two or more.

As the polyhydric alcohol which is one of the alcohol components, ethylene glycol, diethylene glycol, 1,3-propanediol, 2-methyl-1,2
3-propanediol, 1,4-butanediol, 1,
3-butanediol, 2,3-butanediol, dipropylene glycol, 1,5-pentanediol, 1,6
-Hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-1,4-butanediol, 1,7-heptanediol, 1,8-octanediol, 1,9 -Nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane,
2,2-diethyl-1,3-propanediol, 3-methyl-1,4-pentanediol, 2,2-diethyl-
1,3-butanediol, 4,5-nonanediol, triethylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol A
And the like. These exemplified compounds may be used alone or in combination of two or more.

As the epoxy compound which is one of the alcohol components, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, diglycidyl ether of bisphenol A and the like can be used. These exemplified compounds may be used alone or in combination of two or more. Examples of the unsaturated monoalcohol that can be used in place of the alcohol component include glycidyl acrylate and glycidyl methacrylate. These exemplified compounds may be used alone or in combination of two or more.

The epoxy (meth) acrylate used for the vinyl ester resin (epoxy (meth) acrylate resin) in the present invention is usually a polymer obtained by reacting an epoxy resin with an unsaturated monocarboxylic acid. As the epoxy resin, a compound having at least one or more epoxy group in one molecule can be used. Specifically, polyglycidyl ether of polyhydric phenol or polyhydric alcohol, epoxy novolak, epoxidized diolefin, fatty acid Epoxidized products, epoxidized drying oils and the like can be used. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, cinnamic acid and derivatives thereof. These exemplified compounds may be used alone or in combination of two or more. Further, if necessary, it may be modified by adding another monobasic acid and / or polybasic acid.

The urethane (meth) acrylate used in the urethane (meth) acrylate resin in the present invention is a polymer obtained by reacting an unsaturated monoalcohol with a polyisocyanate. Examples of the unsaturated monoalcohol include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, oligoethylene glycol mono (meth) acrylate, oligopropylene glycol mono (meth) acrylate, allyl alcohol and the like. Can be Further, as polyisocyanate, tolylene diisocyanate,
Examples include hydrogenated tolylene diisocyanate, meta-xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate and the like. These exemplified compounds may be used alone or in combination of two or more.

The unsaturated polyester (meth) acrylate used for the unsaturated polyester (meth) acrylate resin in the present invention is obtained by reacting an unsaturated monocarboxylic acid or a derivative thereof with a polyester polyol,
Alternatively, it is a polymer obtained by reacting an unsaturated monoalcohol with a polyester polycarboxylic acid. As the polyester polycarboxylic acid and the polyester polyol, the unsaturated polyester may be used. As the unsaturated monocarboxylic acid or a derivative thereof and the unsaturated monoalcohol, the raw materials of the unsaturated polyester, vinyl ester, and urethane (meth) acrylate can be used as they are.

Examples of the polymerizable monomer to be mixed with the resin solids include styrene, vinyl toluene, p-tert.
Styrene monomers such as -butylstyrene, α-methylstyrene, p-chlorostyrene, p-methylstyrene, p-chloromethylstyrene, divinylbenzene, diallyl phthalate, diallyl isophthalate, triallyl cyanurate, triallyl Allyl ester monomers such as isocyanurate, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic 2-ethylhexyl acid, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, di (meth) acrylic acid adduct of bisphenol A diglycidyl ether, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri ( (Meth) acrylate, glycerin tri (meth)
(Meth) acrylic acid-based monomers such as acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. In particular, when a compound having an unsaturated bond such as a vinyl group or an allyl group, for example, an allyl ether of methylol melamine, an adipate of glycerin diallyl ether, an allyl acetal, an allyl ether of methylol glyoxal urein, or the like is used as a resin composition. It is preferable since air curability can be imparted. One of these polymerizable monomers may be used alone, or two or more of them may be used as a mixture. These polymerizable monomers are
It may be used as a solvent in synthesizing each polymer described above, or may be used as a solvent for a high-viscosity polymer for viscosity adjustment.

The radical-curable resin in the present invention is particularly preferably an unsaturated polyester resin containing an unsaturated polyester having a dicyclopentenyl group and a polymerizable vinyl monomer. By using this unsaturated polyester resin, the curability of the resin composition can be further improved. This is because the unsaturated bond of the dicyclopentenyl group reacts with oxygen in the air to accelerate the curing, resulting in a resin having air-curing properties.

In the present invention, the dicyclopentenyl group is

[0023]

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And / or a substituent represented by

[0025]

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Refers to a substituent represented by The unsaturated polyester may be all or at least partially an unsaturated polyester having a dicyclopentenyl group,
The unsaturated polyester having a dicyclopentenyl group and the above-mentioned ordinary unsaturated polyester may coexist. That is, the unsaturated polyester having a dicyclopentenyl group in the present invention is obtained by replacing at least a part of the raw material of the unsaturated polyester with a compound having a dicyclopentenyl group to introduce a dicyclopentenyl group into the unsaturated polyester. It is obtained.

As a method for incorporating a dicyclopentenyl group into the unsaturated polyester, specifically, for example,
A method in which at least a part of the acid component as a raw material of the unsaturated polyester is replaced with an unsaturated polybasic acid adduct of dicyclopentadiene, and / or at least a part of the alcohol component is a glycol adduct of dicyclopentadiene or a hydride. A method of substituting with xidicyclopentadiene or the like can be given.

Examples of the unsaturated polybasic acid adduct of dicyclopentadiene include adducts obtained by adding the above-mentioned unsaturated polybasic acids to dicyclopentadiene, such as maleic acid adduct of dicyclopentadiene. An unsaturated divalent carboxylic acid adduct of dicyclopentadiene, a maleic acid half ester adduct of dicyclopentadiene, or the like can be used. Among these compounds having a dicyclopentenyl group, an unsaturated divalent carboxylic acid adduct of dicyclopentadiene is preferable, and a maleic acid adduct of dicyclopentadiene is particularly preferable. The maleic acid adduct of dicyclopentadiene can be produced by performing an addition reaction between dicyclopentadiene and maleic anhydride in the presence of water.

Another method for incorporating a dicyclopentenyl group into an unsaturated polyester is, for example, the addition of an acid component or an alcohol component to dicyclopentadiene simultaneously with the condensation polymerization of an acid component and an alcohol component in the unsaturated polyester. To produce a compound having a dicyclopentenyl group. That is, the condensation polymerization is carried out by mixing dicyclopentadiene with the acid component and the alcohol component used for the synthesis of the unsaturated polyester, or after the condensation polymerization is started by mixing the acid component and the alcohol component, Is added.

In the present invention, the content of dicyclopentenyl group in the unsaturated polyester having a dicyclopentenyl group is preferably 5 to 30% by weight based on the skeleton of the unsaturated polyester. When the content of dicyclopentenyl group is less than 5% by weight, the air-curing property becomes insufficient. On the other hand, when the content exceeds 30% by weight, the resin composition becomes hard,
And it becomes brittle, for example FR in combination with glass fiber
In the case of P, molding cracks are likely to occur. On the other hand, when the content of the dicyclopentenyl group is within the above-mentioned preferable range, the air-curing property is excellent, and the FRP exhibits good mechanical strength characteristics.

The dicyclopentenyl group content of the unsaturated polyester having a dicyclopentenyl group is calculated as follows. That is, first, the total weight of the acid component and the alcohol component (including the compound having a dicyclopentenyl group), which are the components forming the ester chain, is calculated by subtracting the weight of the component which is eliminated by condensation of the acid component and the alcohol component. The value obtained is taken as the total weight of the unsaturated polyester having dicyclopentenyl groups.
The number of moles of the compound having a dicyclopentenyl group used is multiplied by the molecular weight of the dicyclopentenyl group (133), and the obtained value is defined as the weight of the dicyclopentenyl group. The value obtained by dividing the weight of the dicyclopentenyl group by the total weight of the unsaturated polyester having the dicyclopentenyl group is defined as the content of the dicyclopentenyl group. In addition,
When a compound having a dicyclopentenyl group is produced during the condensation polymerization, the weight of the compound having a dicyclopentenyl group is determined by the theoretical amount calculated from the weight of the raw materials used for producing the compound having the dicyclopentenyl group. do it.

As a method for synthesizing an unsaturated polyester resin having a dicyclopentenyl group, for example,
technical Proceedings, 36th
Annual Conference, Reinfor
sed Plastics / Composites I
nstate, The Society of
e Plastics Industry In
c. , Session 7-E (1981).

The polymerizable vinyl monomer mainly contained in the unsaturated polyester resin having a dicyclopentenyl group includes, among the polymerizable monomers exemplified above, styrene-based monomers and (meth) acrylic monomers. Acid monomers and the like can be mentioned. In the present invention, the compounding conditions and the like of each raw material of the polymer to be a resin solid content constituting the radical-curable resin,
What is necessary is just to set suitably according to the physical properties etc. of a desired resin hardened material, and it does not specifically limit. Further, the reaction temperature and the reaction time in the condensation polymerization for obtaining each polymer are not particularly limited, and the reaction can be efficiently performed depending on the type and combination of the raw materials, the amount used, and the like. What is necessary is just to set suitably.

In the condensation polymerization of the polymer, a known polymerization inhibitor may be used, if necessary. As the polymerization inhibitor at this time, specifically, for example, hydroquinone,
Methylhydroquinone, methoxyhydroquinone, t-
Examples thereof include, but are not particularly limited to, butylhydroquinone, benzoquinone, t-butylcatechol, catechol, α-naphthol, and nitrophenol.

The condensation polymerization of the polymer can be carried out without a solvent, but a solvent may be used. The type and amount used when a solvent is used are not particularly limited, and may be appropriately selected. The radical-curable resin of the present invention can be adjusted to a desired viscosity by adding a polymerizable monomer to the resin solid content. Generally, the ratio of the resin solid content to the polymerizable monomer in the resin is preferably in the range of 10:90 to 90:10 by weight.

The curable resin composition of the present invention must contain both phenylphosphonic acids and an N-oxyl compound. By using at least two kinds of compounds, phenylphosphonic acids and N-oxyl compounds, excellent storage stability is maintained, and when a curing agent is added, curing properties are not impaired and good at room temperature. It can exhibit excellent curability. N-oxyl compounds exhibit an excellent polymerization inhibiting effect at room temperature, while phenylphosphonic acids have a weak polymerization inhibiting effect, but have an effect of improving the curability when coexisting with a curing agent. It demonstrates. Therefore,
Only by using both of them, sufficient storage stability can be obtained with a small amount of the N-oxyl compound. In addition, when curing is performed, the curing is quickly performed even in a situation where the amount of the curing agent used must be reduced. It can be done.

The phenylphosphonic acids in the present invention are not particularly limited. For example, at least one compound selected from the group consisting of phenylphosphonic acid, phenylphosphonic acid ester, and phenylphosphonic acid chloride is preferable. . These may be used alone or in combination of two or more. Examples of phenylphosphonic acid esters include phenylphosphonic acid dimethyl ester. Further, as phenylphosphonate, for example,
And phenylphosphonic acid dichloride.

In the present invention, the content of phenylphosphonic acids is from 10 to 10 by weight based on the whole resin composition.
Preferably it is 500 ppm. When the content of the phenylphosphonic acids is less than 10 ppm, the effect of improving the curability when a curing agent is added is hardly remarkably exhibited. On the other hand, when the content exceeds 500 ppm, the drying property of the resin composition may be significantly impaired. Because there is.

The N-oxyl compound in the present invention has a compound represented by the general formula (1)

[0040]

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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 an —NR ₇
R ₈ , 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 a carbon atom
16 represents an alkyl group) and the general formula (2)

[0042]

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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 —
Represents NR ₁₅ R _{16 radical, 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 the general formula (3)

[0044]

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(Wherein, R ₁₇ and R ₁₈ each independently represent an alkyl group having 4 or more carbon atoms). The N-
As the oxyl compound, specifically, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine-
1-oxyl, di-t-butylnitroxyl, 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl
Oxyl-2,2,6,6-tetramethylpiperidine-
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 -Tetramethylpiperidin-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-2,2,2) 6,6-tetramethylpiperidin-4-yl) n-butylmalonic acid ester, 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-
Tetramethylpiperidin-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 and the like, but are not particularly limited. These N
As the -oxyl compound, only one kind may be used, or two or more kinds may be appropriately used in combination.

In the present invention, among the N-oxyl compounds exemplified above, particularly, 4-hydroxy-2,2,2
6,6-Tetramethylpiperidine-1-oxyl is preferred. By adding 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, it is possible to maintain a particularly long pot life which shows particularly good storage stability and can be put to practical use.

In the present invention, the content of the N-oxyl compound is from 10 to 100 by weight based on the whole resin composition.
It is preferably 0 ppm. If the content of the N-oxyl compound is less than 10 ppm, the storage stability effect is hardly remarkably exhibited, while if it exceeds 1000 ppm, the curability of the resin composition may be reduced. In the present invention, the radical-curable resin contains a metal compound having a redox effect. Examples of such a compound include metal carboxylate such as metal salt of aliphatic carboxylic acid, metal salt of aromatic carboxylic acid and metal salt of alicyclic carboxylic acid, and metal chelate complex. In particular, cobalt, manganese, tin, vanadium,
A metal compound containing at least one metal selected from the group consisting of copper (hereinafter, referred to as a specific metal) is preferably used. As a metal compound containing a specific metal,
Examples include naphthenates of the specific metal, octenoates of the specific metal, phosphates of the specific metal, acetylacetonate complexes of the specific metal, and the like.

In the present invention, the metal compound having a redox effect is usually used in the range of 0.001 to 2 parts by weight based on 100 parts by weight of the radical curable resin. When the metal compound is in the form of a powder, it may be dissolved in various solvents or polymerizable monomers in consideration of workability to form a solution having a metal content of 1 to 10% by weight, and then added to the resin. . Also,
In the present invention, conventionally known dimethylaniline, acetylacetone, acetoacetic anilide and the like can be used in combination as a curing accelerator in addition to the metal compound having a redox effect. These curing accelerators may be previously contained in the resin composition, or
You may mix immediately before mixing a hardening | curing agent in order to harden a resin composition.

Further, the curable resin composition of the present invention may contain, if necessary, a curing agent, a curing accelerator, a filler, an ultraviolet absorber, a pigment, and a thickening agent for imparting thixotropic properties such as anhydrous silica. And thixotropic stabilizers such as quaternary ammonium salts such as tetramethylammonium chloride and triethylbenzylammonium chloride, low-shrinkage agents, antioxidants,
Various additives such as a plasticizer, an aggregate, a flame retardant, a stabilizer, and a reinforcing agent may be included. The amount of these additives used is
There is no particular limitation.

The method for producing a curable resin composition according to the present invention is, for example, a method for producing a curable resin composition including a step of preparing a radical curable resin containing a metal compound having a redox effect, Phenylphosphonic acids are added in a weight ratio of 10 to 500 p with respect to the whole resin composition.
pm, and the N-oxyl compound is added in an amount of 10 to 1000 ppm by weight based on the entire resin composition.
It is added so that That is, a metal compound having a redox effect, a phenylphosphonic acid, and an N-oxyl compound are added to a radical curable resin produced by an ordinary method. These compounds and other additives may be mixed in any order. In particular, with respect to the phenylphosphonic acids and the N-oxyl compound, the whole or a part thereof can be added in the step of producing the radical-curable resin. In addition, as the method and apparatus for mixing these, the method and apparatus usually used in the art can be used as they are.

[0051]

EXAMPLES Examples and comparative examples according to the present invention will be described below, but the present invention is not limited by these examples. The following "parts" are "parts by weight"
Shall mean. The properties and evaluation of the curable resin compositions obtained in Examples and Comparative Examples were measured by the following methods.

[Viscosity] The viscosity was measured at 25 ° C. by a Brookfield viscometer described in JIS-K-6901. [Index] Measured by the method described in JIS-K-6901. [Normal gel time] According to the coagulation method described in JIS-K-6901, a methyl ethyl ketone peroxide-based catalyst (trade name “Kayamec M” manufactured by Kayaku Co., Ltd.) was used as a catalyst, and the amount added was 1.0%. Or 0.5%, 2
Measured at 5 ° C.

[Hardness] To the curable resin composition, 1.0% or 0.5% of a methyl ethyl ketone peroxide-based catalyst (trade name “Kayamek M” manufactured by Kazaku Akzo Co., Ltd.) was added, and then a glass fiber mat was added. (CM455FA, manufactured by Asahi Fiber Co., Ltd.) Three layers were impregnated and left at 25 ° C. The surface hardness was measured 3 hours and 5 hours after the curable resin composition impregnated material of the glass fiber mat gelled by using a Barcol hardness meter (trade name “hardness meter # 935” manufactured by Barber Coleman). .

[Storage Stability] A 140 cc mayonnaise bottle was filled with 50 g of the curable resin composition, and at the same time, both ends of a soft iron pipe having an outer diameter of 8φ, an inner diameter of 6φ, and a length of 60 cm were measured.
After inserting a screw cut by 5 mm with a -8 die, the container was sealed, stored at 40 ° C., and the state of the contents was visually observed. First, a production example of each polymer used for the radical curable resin will be described.

[Production Example 1 of Polymer] Maleic anhydride 19
6 parts, 278 parts of dicyclopentadiene (purity 95%),
Then, 36 parts of deionized water was charged into a four-necked flask, and an addition reaction was performed at 130 ° C. for 3 hours under a nitrogen stream to obtain a maleic acid adduct of dicyclopentadiene. next,
392 parts of maleic anhydride, 592 parts of phthalic anhydride, and 718 parts of propylene glycol were added and mixed, and a dehydration condensation reaction was performed at 200 ° C. for 8 hours under a nitrogen stream,
Unsaturated polyester 1 having an acid value of 25 and having a dicyclopentenyl group was obtained.

[Production Example 2 of Polymer] phthalic anhydride 296
Parts, 304 parts of tetrahydrophthalic anhydride, 588 parts of maleic anhydride, and 798 parts of propylene glycol.
The mixture was charged in a one-necked flask, and subjected to a dehydration condensation reaction at 200 ° C. for 7 hours under a nitrogen stream.
000 unsaturated polyester 2 was obtained.

[Production Example 3 of Polymer] Phthalic anhydride 148
Parts, 882 parts of maleic anhydride and 798 parts of propylene glycol were charged into a four-necked flask and placed under a nitrogen stream.
A dehydration condensation reaction was carried out at a maximum temperature of 220 ° C. to obtain an unsaturated polyester 3 having an acid value of 25 and a number average molecular weight of 2,100.

[Production Example 4 of Polymer] 173 parts of neopentyl glycol, 347 parts of a 2-mol adduct of bisphenol A-ethylene oxide and 261 parts of isophthalic acid were charged into a four-necked flask and placed at 215 ° C. for 10 hours under a nitrogen stream. When the acid value reached 1, it was cooled to 120 ° C,
Next, 183 parts of fumaric acid was added, the temperature was raised to 200 ° C., and the reaction was carried out for 4 hours.
Cooled to ° C. Further, 46 parts of glycidyl methacrylate was added and the mixture was allowed to stand at 130 ° C. for 3 hours to obtain an unsaturated polyester (meth) acrylate.

[Production Example 5 of Polymer] An epoxy resin having an epoxy equivalent of 189 (trade name “Epiclon 850”) obtained by reacting bisphenol A with epichlorohydrin
458 parts, manufactured by Dainippon Ink and Chemicals, Inc.), 215 parts of methacrylic acid, 0.35 parts of hydroquinone, and 2.1 parts of triethylamine were charged into a four-necked flask, and reacted at 110 ° C. for 6 hours under an oxygen-containing gas stream. Thus, an epoxy (meth) acrylate was obtained.

[Production Example 6 of Polymer] 302 parts of 2-hydroxypropyl methacrylate, 0.1 parts of p-benzoquinone
6 parts, 245 parts of methyl methacrylate, and 0.82 parts of dibutyl dilaurate are charged into a four-necked flask, and 270 parts of a liquid diphenylmethane diisocyanate oligomer (isocyanate equivalent: 135) is placed in an air stream at 60 ° C. for 2 hours. The mixture was added dropwise, and the mixture was stirred at the same temperature for 3 hours after completion of the addition. Furthermore, after raising the temperature to 90 ° C. and stirring for 1 hour,
Upon cooling, a urethane (meth) acrylate resin having a viscosity of 3.0 Stokes / 25 ° C containing urethane (meth) acrylate was obtained.

Examples 1 to 6 and Comparative Examples 1 to 6
Each of the polymers obtained in the above Production Examples, a styrene monomer, and methylhydroquinone were blended at the ratios shown in Tables 1, 2, 3, and 4 to prepare radically curable resins. The mixing ratio of methylhydroquinone shown in Tables 1 and 2 is indicated by the content (ppm) with respect to the entire radical-curable resin obtained.

The radical-curable resin is further added with t-
Butyl catechol, copper naphthenate, anhydrous silica fine particles,
Triethylbenzylammonium chloride, dimethylaniline, cobalt octanoate, 4-hydroxy-2,
2,6,6-tetramethylpiperidine-1-oxyl,
Benzenephosphonic acid and phenothiazine were blended at the ratios shown in Tables 1, 2, 3 and 4 to obtain curable resin compositions, respectively. In addition, the compounding ratio of each raw material other than the radical curable resin shown in Tables 1 to 4 is represented by the content (ppm) with respect to the curable resin composition finally obtained.

The properties, hardness, and storage stability of the obtained curable resin composition were evaluated in Tables 1, 2, 3, and 4.
Are shown below.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

As is clear from Tables 1 to 4, Examples 1 to
The curable resin composition No. 6 had good storage stability and also had excellent curability at room temperature. On the other hand, the curable resin compositions of Comparative Examples 1 to 6 do not contain 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and benzenephosphonic acid. In this case, a gel substance was generated, or the viscosity was increased to an unusable state, resulting in a problem in storage stability. Moreover, the curability at room temperature
It was inferior to the curable resin composition of each example containing 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and benzenephosphonic acid.

For example, comparing Example 1 with Comparative Example 1, the room-temperature gelation time when the catalyst addition amount is 1% and 0.5% is 30 minutes and 70 minutes in Example 1, respectively. In Example 1, since the duration was 30 minutes and 60 minutes, the adjustment range of the gel time was wider in Example 1, and the rate of increase in hardness was faster in Example 1 than in Comparative Example 1. It is clear that No. 1 has better curing reactivity.

[0070]

According to the present invention, it is possible to provide a resin composition having good storage stability and exhibiting good curability at room temperature without impairing the curing properties when curing. it can. Therefore, long-term stable storage of the resin composition is possible, and when the resin composition is cured at room temperature,
Even if the amount of the curing agent added is within a range that can ensure a sufficient pot life, the curing can be performed quickly.
As described above, the curable resin composition of the present invention is suitable for curing at room temperature.
It is useful in the field of molding materials and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/5333 C08K 5/5333 C08L 67/06 C08L 67/06 F-term (Reference) 4J002 BG071 CD201 CF221 CF241 CF251 EA049 EB129 ED029 EE046 EF049 EG046 EG066 EG076 EH079 EH149 ES008 EU028 EU038 EU188 EU189 EU199 EW127 FD038 FD146 FD150 FD157 FD159 FD330 4J027 AB06 AB07 AB08 AB10 AB15 AB16 AB17 AG18 AE23 AG24 AE03

Claims (5)

[Claims] 1. A curable resin composition comprising a radical curable resin and a metal compound having a redox effect, comprising a phenylphosphonic acid and an N-oxyl compound as essential components. Characteristic curable resin composition. 2. The radical-curable resin contains at least one compound selected from the group consisting of unsaturated polyester resins, vinyl ester resins, urethane (meth) acrylate resins, and unsaturated polyester (meth) acrylate resins. The curable resin composition according to claim 1. 3. The curable resin composition according to claim 2, wherein the unsaturated polyester resin comprises an unsaturated polyester having a dicyclopentenyl group and a polymerizable vinyl monomer. 4. The content of the phenylphosphonic acids is 10 to 500 pp by weight relative to the whole resin composition.
m, and the content of the N-oxyl compound is
10 to 1000 ppm by weight based on the whole resin composition
The curable resin composition according to any one of claims 1 to 3, wherein 5. The phenylphosphonic acid is phenylphosphonic acid, phenylphosphonic acid ester,
The curable resin composition according to any one of claims 1 to 4, wherein the curable resin composition is at least one compound selected from the group consisting of phenylphosphonic acid chlorides.