JP2001240651A - Vinyl ester, vinyl ester resin, resin composition and molding material thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl ester that has sufficient flame retardancy and heat resistance and water resistance in addition to excellent flexibility. SOLUTION: The objective vinyl ester bears one or more oxazolidone rings per one molecule on the average. In another embodiment, the objective vinyl ester includes phosphorus atoms and additionally bears one or more oxazolidone rings per one molecule on the average.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a vinyl ester,
The present invention relates to a vinyl ester resin, a resin composition, and a molding material.

[0002]

2. Description of the Related Art When a vinyl ester is used as a radical-curable resin composition, it can give a cured product having excellent basic properties such as heat resistance and water resistance after curing. In the various fields such as building materials, housings, laminates, sealing materials, casting materials, molded parts used for mechanical parts, electronic and electrical parts, vehicles, ships, aircrafts, etc., adhesives, electric insulating paints, etc. It has been used in

[0003] A cured product obtained by curing a resin composition containing a vinyl ester is used to improve strength and durability by improving bending strength, flexural modulus and the like, as well as basic performance such as heat resistance and water resistance. There are many applications that require flexibility, and there is a demand for those that exhibit these performances in a well-balanced manner. However, usually, the chain length of the vinyl ester is lengthened to make the skeleton flexible, or if the flexibility is improved by adjusting the crosslink density of the cured product, heat resistance, water resistance, etc. are reduced. However, these properties cannot be balanced by increasing flexibility while maintaining heat resistance and water resistance.

By the way, such a cured product inherently has a flammable property as an organic substance. Therefore, when it is used for a molded product such as a building material, for example, it is difficult to satisfy fire prevention standards and the like. Flammability must be imparted. Such flame retardancy is usually imparted by blending a flame retardant into the resin composition. However, when a flame retardant is blended, heat resistance and the like are reduced, so that it was not possible to effectively impart flame retardancy while maintaining necessary physical properties.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has a sufficient flame retardancy, heat resistance, water resistance and excellent flexibility. The purpose is to provide.

[0006]

SUMMARY OF THE INVENTION The present invention is a vinyl ester having an average of one or more oxazolidone rings per molecule. The present invention is also a vinyl ester resin containing the vinyl ester and a polymerizable unsaturated monomer. The present invention is also a resin composition containing the vinyl ester resin. The present invention is also a molding material comprising the above resin composition, wherein the resin composition is a molding material containing reinforcing fibers and / or fillers. Hereinafter, the present invention will be described in detail.

[0007] The vinyl ester of the present invention has an average of one or more oxazolidone rings per molecule. Such a vinyl ester has a cured product having sufficient basic properties such as heat resistance and water resistance, and also has excellent flexibility, and these properties are balanced. Therefore, it can be widely used for applications requiring flexibility, and
Since it has sufficient heat resistance, it can effectively and stably provide flame retardancy, and can be used for building materials, housings, laminates, sealing materials, casting materials, mechanical parts,
It can be effectively used in various fields such as electric parts, molded articles used for vehicles, ships, aircrafts, etc., adhesives, and electrically insulating paints.

[0008] In the present specification, vinyl ester means a radically polymerizable oligomer having a polymerizable unsaturated bond and an ester bond. In the present invention, among the above vinyl esters, those in which a polymerizable unsaturated bond is derived from a (meth) acryloyl group and an ester bond is formed by a reaction between (meth) acrylic acid and an epoxy ring are preferably applied. . Such a vinyl ester is sometimes called epoxy (meth) acrylate and has sufficient curability.

The oxazolidone ring in the molecule of the vinyl ester may be present at any position in the molecule of the vinyl ester, and is not particularly limited. For example, the vinyl ester has heat resistance, water resistance and flexibility. It is preferable that two oxazolidone rings are bonded by a divalent organic group having 6 to 20 carbon atoms in order to achieve an excellent balance between the two groups. More preferably, all the oxazolidone rings in the molecule are in the form described above.

The number of oxazolidone rings present in the molecule of the vinyl ester is 1 on average per molecule.
The number is not particularly limited as long as the number is at least one, but is preferably 1 to 10 on average per molecule, and may be appropriately set according to the basic performance such as flexibility required for the vinyl ester. The number is more preferably 1 to 5, and even more preferably 1.5 to 3.

The vinyl ester has a number average molecular weight (M
n) is not particularly limited and may be, for example, 500 to 300.
It is preferably 0. If it is less than 500, the basic performance such as the strength of the cured product may be inferior. If it exceeds 3000, the viscosity of the resin composition may increase and the workability may decrease. More preferably, it is 700-2000.

The vinyl ester is obtained by reacting an epoxy resin having an average of one or more oxazolidone rings per molecule (hereinafter referred to as an epoxy resin having an oxazolidone ring) with an unsaturated monobasic acid as essential components. It is preferred that As a result, a vinyl ester having one or more oxazolidone rings on average per molecule can be easily and efficiently prepared, and can be industrially advantageously supplied. Further, such a vinyl ester has an excellent balance between heat resistance, water resistance and flexibility, and can effectively impart flame retardancy.

The epoxy resin having an oxazolidone ring is not particularly limited.
Epoxy resins and the like that can be obtained by reacting a compound or oligomer having two molecules per molecule with a diisocyanate, and it is easy to obtain and prepare raw materials,
Since the vinyl ester has an excellent balance of heat resistance, water resistance and flexibility, an epoxy resin represented by the following general formula (1) obtained by reacting a bisphenol type epoxy resin with a diisocyanate is used. Preferably, it is used. These may be used alone or in combination of two or more.

[0014]

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In the above general formula (1), X represents a structure of the following general formula (2). Y represents a divalent organic group having 6 to 20 carbon atoms, and is a residue excluding an isocyanate group derived from diisocyanate. n represents an integer of 0 or more.

[0016]

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In the above general formula (2), Z is -CH_Two −,
-CH (CH_Three )-, -C (CH_Three ) _Two -Or -SO_Two 
-Represents a divalent organic group. m represents an integer of 0 or more.
Bisphenol type epoxy resin and diisocyanate
Reaction with bisphenol epoxy resin
Is not particularly limited. For example, bisphenol A type epoxy
Xy resin, bisphenol F type epoxy resin, bisphen
It is possible to use a nol S type epoxy resin or the like. Ma
The diisocyanate is not particularly limited.
For example, tolylene diisocyanate, diphenylmethane dii
Socyanate, xylylene diisocyanate, isophoro
Diisocyanate, hexamethylene diisocyanate
Etc. can be used. These are used alone
Or two or more of them may be used in combination.

The reaction between the above bisphenol type epoxy resin and diisocyanate is described, for example, in JP-A-48-103.
570, JP-A-49-37999, JP-A-49-94798, JP-A-49-93491, JP-A-50-136398, and JP-A-50-1
The reaction can be carried out in the same manner as in the reaction conditions described in 17771.

As the epoxy resin having an oxazolidone ring, commercially available products can be used. Examples of such commercially available products include Araldite AER415 manufactured by Asahi Ciba.
2. Araldite XAC4151 (all are trade names)
ACR epoxy R-12 manufactured by AC R
06, ACR epoxy R-1348 (all are trade names)
And the like.

The average epoxy equivalent of the epoxy resin having an oxazolidone ring is not particularly limited, but is preferably, for example, 300 to 1,000. 1000
If it exceeds 3, the viscosity of the resin composition increases, and the workability decreases. More preferably, it is 300 to 700.

The unsaturated monobasic acid to be reacted with the above-mentioned epoxy resin having an oxazolidone ring is not particularly restricted but includes, for example, (meth) acrylic acid, cinnamic acid, crotonic acid, sorbic acid, monomethylmalate and monobutylmale. And a half ester of an unsaturated dibasic acid such as a salt. These may be used alone or in combination of two or more.

The reaction ratio between the epoxy resin having an oxazolidone ring and the unsaturated monobasic acid is not particularly limited. For example, one equivalent of the epoxy group of the epoxy resin having an oxazolidone ring may be used with respect to one equivalent of the unsaturated monobasic acid. It is preferable to set so that the acid group of may be 0.9 to 1.1 equivalent.

In the reaction between the epoxy resin having an oxazolidone ring and the unsaturated monobasic acid, it is preferable to add a reaction catalyst in order to promote the reaction without causing gelation. It is preferable to add a polymerization inhibitor or molecular oxygen to prevent gelation during the reaction. The reaction catalyst is not particularly limited, and examples thereof include amines such as triethylamine and benzyldimethylamine, and acid adducts of these amines; quaternary ammonium salts such as tetramethylammonium chloride and triethylbenzylammonium chloride; amides Imidazoles; pyridines; phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide and ethyltriphenylphosphonium bromide; sulfonium salts; sulfonic acids; and organic metal salts such as zinc octylate. These may be used alone or in combination of two or more.

The amount of the reaction catalyst used is not particularly limited, and may be, for example, 0.00 to the total weight of the reaction raw materials.
It is preferable to set the amount to be 5 to 3.0% by weight. If it is less than 0.005% by weight, the reaction may not be sufficiently promoted. If it exceeds 3.0% by weight, the reaction will not be further promoted. More preferably, 0.05 to
1.0% by weight. In addition, in this specification, a reaction raw material means a raw material that will constitute a vinyl ester.

The polymerization inhibitor is not particularly limited.
For example, hydroquinone, methylhydroquinone, p-
t-butylcatechol, 2-t-butylhydroquinone, trimethylhydroquinone, p-benzoquinone, naphthoquinone, methoxyhydroquinone, phenothiazine, methylbenzoquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-butylbenzoquinone , 4
-Hydroxyl-2,2,6,6-tetramethylpiperidine-1-oxyl and the like. These may be used alone or in combination of two or more.

The molecular oxygen is not particularly limited.
For example, air; a mixed gas of air and an inert gas such as nitrogen; In this case, it may be used by blowing into the reaction system (so-called bubbling). In order to sufficiently prevent gelation due to the above reaction, it is preferable to use a polymerization inhibitor and molecular oxygen in combination.

In the above reaction, if necessary,
A polymerizable unsaturated monomer or solvent inert to the reaction may coexist. The reaction conditions in the above reaction are not particularly limited. For example, the reaction temperature and the reaction time may be appropriately set so that the reaction is completed.

The number average molecular weight (Mn) per (meth) acryloyl group in a vinyl ester obtained by reacting the epoxy resin having an oxazolidone ring and an unsaturated monobasic acid as essential components is not particularly limited. For example, it is preferably from 200 to 3000. 200
If less than the toughness of the cured product may be reduced,
If it exceeds 3,000, the heat resistance and water resistance of the cured product may decrease. More preferably, it is 200 to 1,000.

The above vinyl ester has flame retardancy by having a phosphorus atom. Such a vinyl ester has a cured product having sufficient basic properties such as heat resistance and water resistance, has excellent flexibility, and has sufficient flame retardancy. The oligomer can be suitably used for various applications that require a balance between heat resistance, water resistance, and flexibility and flame retardancy.

The vinyl ester having a phosphorus atom is
A phosphorus atom is incorporated in at least one of the molecules included therein, for example, in the above-described reaction between an epoxy resin having an oxazolidone ring and an unsaturated monobasic acid, a compound having a phosphorus atom is used in combination. Can be obtained.

The compound having a phosphorus atom is not particularly limited, and for example, a compound having an acid group is preferable. Such compounds include, for example, alkylphosphonic acid, arylphosphonic acid, (carboxyalkyl) alkylphosphinic acid, (carboxylalkyl) arylphosphinic acid, acidic phosphoric acid ester, 9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10
-Oxide and the like. These may be used alone or in combination of two or more.

In the reaction for obtaining the vinyl ester having a phosphorus atom, the reaction ratio of the epoxy resin having an oxazolidone ring, the unsaturated monobasic acid, and the compound having a phosphorus atom is not particularly limited. It is preferable to set the total of the acid group of the unsaturated monobasic acid and the acid group of the compound having a phosphorus atom to be 0.9 to 1.1 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. . In addition, the reaction ratio between the acid group of the unsaturated monobasic acid and the acid group of the compound having a phosphorus atom is, for example, one equivalent of the acid group of the unsaturated monobasic acid to the acid group of the compound having a phosphorus atom. It is preferable to set so as to be 1 equivalent or less. If the acid group of the compound having a phosphorus atom exceeds 1 equivalent, the curability of the resin composition may decrease, or the heat resistance and water resistance of the cured product may decrease.

The content of the phosphorus atom in the vinyl ester having a phosphorus atom is not particularly limited, and is preferably, for example, 1.5 to 15.0% by weight.
If the amount is less than 1.5% by weight, the cured product may not have sufficient flame retardancy. If the amount exceeds 15.0% by weight, the cost of the vinyl ester may increase. More preferably, it is 2.5 to 10.0% by weight, and still more preferably 3.5 to 7.0% by weight.

By mixing the vinyl ester of the present invention with a polymerizable unsaturated monomer, a vinyl ester resin is obtained. Such a vinyl ester resin can be suitably used as a radical polymerizable resin for various applications that require a balance between heat resistance, water resistance, and flexibility. Such a vinyl ester resin is also one of the present invention.

The polymerizable unsaturated monomer is not particularly limited, and is not particularly limited as long as it has an unsaturated bond capable of undergoing a polymerization reaction with a vinyl ester, for example, styrene, α-methyl Styrene, vinyl toluene,
Divinylbenzene, diallylphthalate, N-vinylpyrrolidone, (meth) acrylic acid, methyl (meth) acrylate, ethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate, 1,6
-Hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like. These may be used alone or in combination of two or more.

In the vinyl ester resin, the content ratio of the vinyl ester and the polymerizable unsaturated monomer is not particularly limited. For example, (weight of vinyl ster / weight of polymerizable unsaturated monomer) is 10 / It is preferably 90 to 80/20. The content ratio of vinyl stell is 10/90.
If the amount is less than the above, the basic performance such as the strength of the cured product may be reduced. If the amount exceeds 80/20, the viscosity of the resin composition may be increased and the workability may be reduced. More preferably, it is 20/80 to 70/30.

The vinyl ester resin may further contain other radically polymerizable oligomers, if necessary. Such a radical polymerizable oligomer is not particularly limited, and examples thereof include unsaturated polyester, epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate. These may be used alone or in combination of two or more. In addition, the said epoxy (meth) acrylate means a thing different from the vinyl ester of this invention.

When the vinyl ester resin is used for applications requiring flame retardancy, the vinyl ester resin preferably contains 0.5 to 12.0% by weight of phosphorus atoms. If the amount is less than 0.5% by weight, the cured product may not have sufficient flame retardancy. If the amount exceeds 12.0% by weight, the cost of the vinyl ester resin may increase. More preferably, it is 1.0 to 8.0% by weight, and still more preferably, 2.0 to 6.0% by weight.

The method for adding a phosphorus atom to the vinyl ester resin is not particularly limited.
1) A method using a vinyl ester having a phosphorus atom; (1-2) A method of blending a radical polymerizable oligomer or a polymerizable unsaturated monomer having a phosphorus atom;
A method in which 1) and (1-2) are used in combination is exemplified.

In the above method (1-2), the radically polymerizable oligomer having a phosphorus atom is not particularly limited. For example, unsaturated polyester, epoxy (meth) acrylate, urethane ( (Meth) acrylate, polyester (meth) acrylate and the like. Moreover, it does not specifically limit as a polymerizable unsaturated monomer which has a phosphorus atom, For example, 2- (meth) acryloyloxyethyl acid phosphate etc. are mentioned. These may be used alone, respectively.
Two or more kinds may be used in combination.

A resin composition is obtained by mixing the above-mentioned vinyl ester resin with a compound constituting the composition.
Such a resin composition can be suitably used as a radically polymerizable resin composition for various applications that require a balance between heat resistance, water resistance, and flexibility. Such a resin composition is also one of the present invention.

When the above resin composition is used for applications requiring flame retardancy, the resin composition contains a phosphorus atom in an amount of 0.1%.
It is preferred to have 1 to 7.0% by weight. 0.1% by weight
If it is less than 7, the cured product may not have sufficient flame retardancy. If it exceeds 7.0% by weight, the flame retardancy of the cured product is further improved, but the heat resistance and water resistance of the cured product are poor. It may decrease. More preferably, it is 0.3 to 6.0% by weight, and still more preferably, 0.5 to 5.0% by weight.

The method for incorporating a phosphorus atom into the resin composition is not particularly limited. For example, (2-1) a method using the vinyl ester resin containing the phosphorus atom;
(2-2) A method of blending a non-reactive addition type phosphorus compound; a method of using the above (2-1) and (2-2) in combination. Among them, it is preferable to use the method (2-1), since flame retardancy can be stably imparted to the cured product.

In the above method (2-2), the non-reactive addition type phosphorus compound is not particularly limited.
Triphenyl phosphate, cresyl diphenyl phosphate, resorcinol diphenyl phosphate, PX
-200 (trade name, manufactured by Daihachi Chemical Co., Ltd.); and phosphorus-amino complex compounds such as ammonium polyphosphate, melamine phosphate, and guanidine phosphate. These may be used alone or in combination of two or more. In order to further improve the flame retardancy of the resin composition, a halogen-based flame retardant or a nitrogen-based flame retardant; a boron-based flame retardant or the like can be blended. Since the cured product may cause environmental pollution due to dioxin at the time of combustion, it is preferable to impart nonflammable flame retardancy.

It is preferable to add a curing agent to the resin composition, since the resin composition can be easily cured by heating or irradiation with active energy rays such as ultraviolet rays, electron beams, and radiations. When the resin composition is cured by heating, as a curing agent that imparts thermosetting properties to the resin, for example, diisopropyl peroxydicarbonate, t-
Butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,
1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxyneodikenate, lauryl peroxide, benzoyl peroxide, 1 , 1-bis (t-butylperoxy) -3,3,
5-trimethylcyclohexanone, cyclohexanone peroxide, t-butylperoxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide And organic peroxides such as t-butyl hydroperoxide; and azo compounds such as azobisisobutyronitrile and azobisdiethylvaleronitrile. These may be used alone or in combination of two or more.

When the above resin composition is cured by ultraviolet rays, a known photopolymerization initiator and, if necessary, a photosensitizer can be used as a curing agent for imparting photocurability to the resin. The amount of the curing agent is not particularly limited. For example, both the curing agent that imparts thermosetting to the resin and the curing agent that imparts photocuring to the resin are vinyl ester resins 1
Preferably, the amount is 0.1 to 5.0 parts by weight based on 00 parts by weight. The resin composition further, if necessary,
Reinforcing fibers, fillers, pigments, coloring agents, flame retardants,
An antifoaming agent, a wetting agent, a dispersing agent, a rust inhibitor, an antistatic agent, a thermoplastic resin, an elastomer, and the like can be blended, and the blending amounts may be appropriately set according to the application.

The method for curing the resin composition is not particularly limited. For example, in the case of curing by heating, the curing temperature is set at 6
The temperature is preferably set to 0 to 300 ° C. More preferably,
80-250 ° C. In addition, in the case of curing with active energy rays such as ultraviolet rays, a method generally used in the past can be applied. , An excimer lamp or the like can be used. Further, in curing with an electron beam, for example, a scanning type electro-curtain type, a curtain type, a laminar type, an area beam type, a broad beam type, a pulse beam type, or the like can be used as an electron beam irradiation device.

A molding material comprising the above resin composition, wherein the resin composition contains a reinforcing fiber and / or a filler is used as a material for forming a molding.
It can be suitably used for applications requiring a balance between heat resistance, water resistance and flexibility. Such a molding material is also one of the present invention. By blending a reinforcing fiber and / or a filler with the resin composition, it is possible to improve the basic performance such as water resistance and strength and the flame retardancy of the molded product formed from the molding material.

The reinforcing fibers are not particularly limited, and include, for example, inorganic fibers such as glass fibers and carbon fibers;
Organic fibers such as phenol, Teflon, aramid, and polyester are included. These may be used alone,
More than one species may be used in combination. The shape of the reinforcing fiber is not particularly limited and may be, for example, a cloth; a mat shape such as a chop strand mat, a preformable mat, a continuous strand mat, a surfacing mat; a chop shape; a roving shape; And the like. In the present specification, blending a reinforcing fiber with a resin composition means, for example, mixing a reinforcing fiber into a resin composition; impregnating a reinforcing fiber with the resin composition, and the like.

The amount of the reinforcing fibers is not particularly limited as long as it is appropriately set according to the application, and is, for example, preferably 10 to 150 parts by weight with respect to 100 parts by weight of the vinyl ester resin. If the amount is less than 10 parts by weight, the strength of the molded article may be insufficient, and if it exceeds 150 parts by weight, the water resistance and chemical resistance of the molded article may be reduced. More preferably, it is 20 to 75 parts by weight.

The filler is not particularly restricted but includes, for example, aluminum hydroxide, calcium carbonate, barium sulfate, alumina, metal powder, kaolin clay, talc, milled fiber, quartz sand, diatomaceous earth, crystalline silica, fused silica, glass Powder, clay and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use aluminum hydroxide because the moldability is excellent and the flame retardancy is greatly improved.

The amount of the filler is not particularly limited as long as it is appropriately set according to the intended use. For example, it is preferably 30 to 400 parts by weight based on 100 parts by weight of the vinyl ester resin. If the amount is less than 40 parts by weight, the flame retardancy may decrease particularly in applications requiring flame retardancy, and if it exceeds 400 parts by weight, the basic performance such as water resistance and strength of the cured product decreases. There is a risk. More preferably, it is 40 to 300 parts by weight. The molding material is
By the curing method described above, it can be cured and molded into a molded product, and can be used for building materials, housings, laminates, sealing materials, casting materials, mechanical parts, electronic / electric parts, vehicles, ships, aircraft, and the like. It can be used effectively in various fields.

[0053]

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

Synthesis Example 1 A four-necked flask equipped with a thermometer, a stirrer, a gas injection pipe and a reflux condenser was used as a reaction vessel, and araldite was used as an epoxy resin having an average of one or more oxazolidone rings per molecule. 670 parts of AER4152 (trade name, manufactured by Asahi Ciba, average epoxy equivalent: 335), 172 parts of methacrylic acid as an unsaturated monobasic acid, 0.12 part of hydroquinone as a polymerization inhibitor, and 2.4 parts of triethylamine as a reaction catalyst After charging, the mixture was reacted at 115 ° C. in an air stream for 5.0 hours to obtain a vinyl ester (1) according to the present invention having an acid value of 6.0 mgKOH / g and a number average molecular weight (Mn) of 740. Further, 360 parts of styrene was added as a polymerizable unsaturated monomer to obtain a vinyl ester resin (1) according to the present invention.

Synthesis Example 2 Araldite AER41 was placed in the same reaction vessel as in Synthesis Example 1.
52 670 parts, 158 parts of phenylphosphonic acid, and
2.6 parts of triethylamine was charged and reacted at 115 ° C. in an air stream for 3.5 hours. Further, 86 parts of methacrylic acid and 0.13 part of hydroquinone were further added and reacted at 115 ° C. for 4.5 hours in an air stream to obtain an acid value of 4.0.
A vinyl ester (2) according to the present invention having a mg KOH / g and a number average molecular weight (Mn) of 1480 was obtained. In addition to this
By mixing 390 parts of styrene as a polymerizable unsaturated monomer, a vinyl ester resin (2) according to the present invention was obtained. The phosphorus atom content in the vinyl ester resin (2) was 2.4% by weight.

Synthesis Example 3 In the same reaction vessel as in Synthesis Example 1, Araldite AER25 was added.
370 parts, 172 parts of methacrylic acid, 0.08 part of hydroquinone, and 1.5 parts of triethylamine, and charged at 115 ° C. The reaction was carried out in an air stream for 6.0 hours to obtain a vinyl ester (3). Further, 232 parts of styrene was added to obtain a vinyl ester resin (3).

Synthesis Example 4 Alardite AER25 was placed in the same reaction vessel as in Synthesis Example 1.
0 305 parts, Araldite AER6071 (trade name,
Asahi Ciba, bisphenol A type epoxy resin, average epoxy equivalent 460) 365 parts, methacrylic acid 172 parts,
0.128 parts of hydroquinone and 2.4 parts of triethylamine were charged and reacted at 115 ° C. in an air stream for 6.0 hours to obtain a vinyl ester (4). In addition to this
Mixing 360 parts of styrene, vinyl ester resin (4)
I got

Synthesis Example 5 Araldite AER25 was placed in the same reaction vessel as in Synthesis Example 1.
0 370 parts, 158 parts of phenylphosphonic acid, and 1.8 parts of triethylamine were charged and reacted at 115 ° C. in an air stream for 3.0 hours. Further, 86 parts of methacrylic acid and 0.09 part of hydroquinone were added to add 1 part.
The reaction was carried out at 15 ° C. for 4.0 hours in an air stream to obtain a vinyl ester (5). Further, 263 parts of styrene was blended as a polymerizable unsaturated monomer to obtain a vinyl ester resin (5). In addition, the content of the phosphorus atom in the vinyl ester resin (5) was 3.5% by weight.

Examples 1 to 6, Comparative Examples 1 to 4 Vinyl ester resins (1) obtained in Synthesis Examples 1 to 5
(5) PX-200 (trade name, manufactured by Daihachi Chemical Industry Co., Ltd., phosphate ester) as a phosphorus compound was blended according to the composition shown in Table 1, and the mixture was uniformly stirred. Perbutyl Z (product name,
The resin compositions (1) to (6) according to the present invention and the comparative resin compositions (1) to (4) are obtained by adding 1.0 part of Nippon Yushi Co., Ltd. and mixing uniformly. Was. These are placed in a hot air circulating drying oven at 100 ° C. for 30 minutes, then
Cured at 75 ° C. for 30 minutes. The mechanical strength of the obtained cured product was measured according to JIS K6911, and the glass transition point temperature was determined to be TMA (Thermal Mechanical).
(Analyzer). The results are shown in Table 1.

[0060]

[Table 1]

Examples 7 to 12, Comparative Examples 5 to 8 Resin compositions (1) to (6) obtained in Examples 1 to 6 and comparative resin compositions obtained in Comparative Examples 1 to 4 (1)-
In 100 parts of (4), 150 parts of Hygilite H-32I (trade name, manufactured by Showa Denko KK, aluminum hydroxide) and 1.0 part of Parkmill H-80 (trade name, manufactured by NOF CORPORATION) are used as fillers. Was mixed and uniformly stirred. Furthermore, this was cut into a glass cloth (WF
230N100 (trade name, manufactured by Nitto Boseki Co., Ltd.) so as to be 20 g per sheet, and the molding materials (1) to (6) according to the present invention and the comparative molding materials (1) to (4).
I got Next, four layers each of the above molding materials were laminated on a PET film having a thickness of 125 μm, and the PET films were further laminated. This laminated molding material is placed in a hot air circulating drying oven at 100 ° C. for 30 minutes, and further at 175 ° C. for 30 minutes.
Cured for minutes. After curing, the film was cooled to room temperature, and the PET film was removed to obtain molded articles. The obtained molded product was evaluated by the following evaluation methods. The results are shown in Table 2.

[0062]Evaluation method  (1) Flame retardancy Evaluation of flame retardancy conforms to UL Subject 94V method.
I went there. (2) Hot water resistance The obtained molded product is immersed in hot water of 95 ± 3 ° C for a predetermined time.
Each time, take out the whitened state of the molded product after immersion according to the following criteria
Was visually observed and evaluated. A: No whitening and no change. ：: slight whitening, but almost no change Δ: Partly whitened. ×: The whole is whitened.

[0063]

[Table 2]

In Table 2, Example 1, Comparative Examples 5 and 6 were not evaluated for flame retardancy. As is clear from Table 2, in Example 1, it was found that the resin composition of the present invention had both high flexibility and high Tg. On the other hand, Comparative Example 1 had the same Tg but was brittle, and Comparative Example 2 had the same flexibility but low Tg, and all had poor balance. In Examples 7 to 12,
It has been found that the molding material of the present invention can achieve high flame retardancy even with a low phosphorus content and can maintain high water resistance. On the other hand, when the phosphorus content of Comparative Example 7 is small, sufficient flame retardancy cannot be obtained, and when the phosphorus content of Comparative Example 8 is increased, the flame resistance is improved but the water resistance is reduced. I understand.

[0065]

Since the vinyl ester of the present invention has the above-mentioned constitution, it has sufficient basic properties such as heat resistance and water resistance, is excellent in flexibility, and has effective and stable flame retardancy. Building materials, housings, laminates, sealing materials, casting materials, and molded parts used in mechanical parts, electronic and electrical parts, vehicles, ships, aircraft, etc., It can be used effectively in various fields such as adhesives and electric insulating paints.

Continued on front page F-term (reference) 4J002 BD152 BE062 CC042 CD201 CF002 CL062 DA017 DE147 DE237 DG047 DJ017 DJ037 DJ047 DL007 EA046 FA017 FA042 FA047 GF00 GL00 GM00 GN00 GQ00 4J027 AE05 BA05 BA06 BA07 BA15 BA20 BA21 CC22 AD08 AD21 CA20 CA21 CB20 CC02 EA04 FA03 FA05 FB02 FB11 FB13 HA02

Claims (7)

[Claims] 1. A vinyl ester having at least one oxazolidone ring per molecule on average. 2. The vinyl ester according to claim 1, wherein an epoxy resin having an average of one or more oxazolidone rings per molecule and an unsaturated monobasic acid are reacted as essential components. 3. The vinyl ester according to claim 1, which has a phosphorus atom. 4. A vinyl ester resin comprising the vinyl ester according to claim 1, 2 or 3, and a polymerizable unsaturated monomer. 5. A resin composition comprising the vinyl ester resin according to claim 4. 6. The resin composition according to claim 5, comprising 0.1 to 7.0% by weight of a phosphorus atom. 7. A molding material comprising the resin composition according to claim 5, wherein the resin composition comprises reinforcing fibers and / or
Alternatively, a molding material comprising a filler.