JP2001151855A - Method for producing phosphorus-containing vinyl ester and method for producing radically polymerizable resin using the vinyl ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing phosphorus-containing vinyl ester capable of being easily producing the phosphorus-containing vinyl ester from an epoxide compound, a phosphorus-containing compound and (meth)acrylic acid by a simple and easy manufacturing process. SOLUTION: In a method for producing a phosphorus-containing vinyl ester by reacting raw materials containing an epoxide compound, a phosphorus- containing compound and (meth)acrylic acid, the reaction among the epoxy resin, the phosphorus-containing resin and (meth)acrylic acid is simultaneously carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a phosphorus-containing vinyl ester and a method for producing a radically polymerizable resin composition using the vinyl ester, and is particularly suitable for preparing a resin varnish for producing a laminate. It is related to what can be used for.

[0002]

2. Description of the Related Art In manufacturing a laminated board, a continuous method has been put to practical use in which the steps from impregnation of a base material with resin varnish to molding are continuously performed.

FIG. 1 shows an example of an apparatus for the continuous construction method of a laminated board. First, while continuously feeding a long base material 1 wound on a roll, the base material 1 is passed through a resin impregnation tank 2.
Is impregnated with a resin varnish, and a plurality of substrates 1 impregnated with the resin varnish are passed through a roll 3 while being continuously fed. At this time, a long metal foil 4 such as a copper foil is continuously fed at the same time, and is passed over the roll 3 while being superimposed on and below the substrate 1. Then, the base material 1 and the metal foil 4 are passed through a heat-curing furnace 5 to cure the resin varnish impregnated in the base material 1, thereby forming a plurality of base materials 1 and the metal foil 4.
Are laminated and integrated, and after the laminate is drawn out of the heating and curing furnace 5, the laminate is cut into predetermined dimensions by a cutting device 6, whereby a laminate A can be obtained. Here, in a composite laminate such as CEM-3,
Using glass woven fabric 1a and glass nonwoven fabric 1b as base materials,
A glass woven fabric 1a impregnated with a resin varnish on the outside,
It is manufactured by laminating a glass nonwoven fabric 1b impregnated with a resin varnish inside.

When a laminate is formed by a continuous method as described above, a resin varnish impregnated in a substrate is heat-cured in a heat-curing furnace under no pressure. Therefore, as a resin varnish,
What mainly contains a radical polymerization type resin which does not contain a solvent serving as a volatile component and does not generate moisture or other volatile components along with a curing reaction is mainly used. In order to make the laminate flame-retardant, it is necessary to incorporate halogen such as bromine or chlorine into the skeleton of the radically polymerizable resin.

However, when a laminate is manufactured using a radical polymerization type resin containing halogen such as bromine or chlorine, when the laminate is burned, bromine and chlorine contained in the resin skeleton are reduced. Dissociation generates toxic gas such as hydrogen bromide gas, hydrogen chloride gas, or dioxin, which has a problem that it may affect the human body and the environment.

Accordingly, a raw material containing an epoxide compound, a phosphorus-containing compound and (meth) acrylic acid is reacted to form a phosphorus-containing vinyl ester, and a resin varnish is prepared from the resin composition containing the phosphorus-containing vinyl ester. Thus, it has been considered to obtain a laminated board which can be made flame-retardant without having to contain halogen such as bromine or chlorine.

Here, the following method has been proposed for producing such a phosphorus-containing vinyl ester.

First, a phosphorus-containing compound (10- (2,5-dihydroxyphenyl) -10H) is placed in a four-necked flask having an appropriate volume in which a condenser, a stirrer, and a thermometer are set.
-9-oxa-10-phosphaphenanthrene-10-
Oxide; manufactured by Sanko Co., Ltd .; "HCA-HQ") 88.
2 g and 177.5 g of an epoxide compound (manufactured by Yuka Shell Epoxy Co .; "Epicoat 152") are mixed, and the reaction mixture is heated using an oil bath.

When the temperature of the reaction mixture reaches 100 ° C., 0.53 g of triphenylphosphine is added as a catalyst to start the reaction.

After the start of the reaction, the mixture is heated to 125 ° C.
The reaction is allowed to proceed for 5 hours.

When it is confirmed that the acid value in the solution has become 1.0 or less, 0.25 g of hydroquinone is added to prevent runaway of the reaction, and 79.8 g of styrene is added to reduce the viscosity of the solution. .

Next, 52.7 g of methacrylic acid are added, the flask is heated again and 0.32 g of triphenylphosphine are added as additional catalyst.

In this state, the temperature of the solution is kept at 120 ° C., and the reaction proceeds.

During the course of the reaction, the progress of the reaction is traced by measuring the acid value in the solution as needed. When the acid value reaches the range of 11 to 13, the reaction is considered to be completed, and 140.8 g of styrene is added. To dilute and cool the solution.

By performing the above operations, a phosphorus-containing vinyl ester is formed in the flask.

[0016]

However, in the method for producing a phosphorus-containing vinyl ester as described above, an operation of reacting an epoxide compound with a phosphorus-containing compound to advance a reaction for modifying the epoxide compound includes the steps of: A two-step operation is required, in which methacrylic acid is added to the modified epoxide compound to advance a reaction for generating a phosphorus-containing vinyl ester, and the production process becomes complicated, resulting in poor production efficiency. there were.

The present invention has been made in view of the above points, and has been made in view of the above circumstances.
From acrylic acid, a phosphorus-containing vinyl ester, a method for producing a phosphorus-containing vinyl ester that can be easily produced in a simple production process, and using this phosphorus-containing vinyl ester, suitable as a resin varnish for laminate production It is an object of the present invention to provide a method for producing a radically polymerizable resin composition that can be used for the method.

[0018]

The method for producing a phosphorus-containing vinyl ester according to claim 1 of the present invention comprises producing a phosphorus-containing vinyl ester by reacting a raw material containing an epoxide compound, a phosphorus-containing compound and (meth) acrylic acid. In the method, the reaction of the epoxy resin, the phosphorus-containing compound and the (meth) acrylic acid is performed simultaneously.

According to a second aspect of the present invention, in addition to the first aspect, a raw material containing an epoxide compound, a phosphorus-containing compound and (meth) acrylic acid is mixed, and the reaction is started by adding a catalyst. It is assumed that.

According to a third aspect of the present invention, in addition to the first or second aspect, a phosphorus-containing compound represented by the following chemical structural formula (1) is used as the phosphorus-containing compound. It is.

[0021]

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According to a fourth aspect of the present invention, in addition to any one of the first to third aspects, the epoxide compound, the phosphorus-containing compound and the (meth) acrylic acid have a total amount of 8 to 75 parts by mass. It is characterized by using parts by weight of a phosphorus-containing compound.

According to a fifth aspect of the present invention, in addition to any one of the first to fourth aspects, the epoxide compound, the phosphorus-containing compound and the (meth) acrylic acid have a total amount of 10 to 60 parts by mass. It is characterized in that novolak type epoxy resin in parts by mass is used.

According to a sixth aspect of the present invention, in addition to any one of the first to fifth aspects, as the phosphorus-containing compound, a phosphorus-containing compound represented by the following chemical structural formula (2): It is characterized by using at least one of the phosphorus-containing compounds represented by (3).

[0025]

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[0026]

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According to a seventh aspect of the present invention, there is provided a method for producing a radically polymerizable resin composition, wherein the phosphorus-containing vinyl ester obtained by the method according to any one of the first to sixth aspects is added to a metal water. Oxides, phosphates and 3 per molecule
At least one of substances having two or more radical polymerizable double bonds is compounded.

The invention of claim 8 is characterized in that, in addition to the constitution of claim 7, 30 to 465 parts by weight of a metal hydroxide is added to 100 parts by weight of the phosphorus-containing vinyl ester. is there.

According to a ninth aspect of the present invention, in addition to the constitution of the seventh or eighth aspect, 5 to 40 parts by mass of a phosphoric acid ester is added to 100 parts by mass of the phosphorus-containing vinyl ester. It is.

The tenth aspect of the present invention provides the seventh to ninth aspects.
In addition to any one of the above, the phosphorus-containing vinyl ester 1
It is characterized in that a substance having three or more radically polymerizable double bonds in one molecule of 5 to 105 parts by mass with respect to 00 parts by mass is compounded.

[0031]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a phosphorus-containing vinyl ester is produced from a raw material containing an epoxide compound, a phosphorus-containing compound and (meth) acrylic acid. The notation (meth) acrylic acid in this specification indicates one or both of acrylic acid and methacrylic acid.

Further, in the present invention, such a phosphorus-containing vinyl ester is used as a radical polymerizable resin, and further, a radical polymerizable monomer such as styrene or diallyl phthalate, a radical polymerization initiator, and a filler, if necessary. To prepare a radically polymerizable resin composition.

From the radically polymerizable resin composition thus obtained, a resin varnish for producing a laminate can be prepared and obtained. The resin varnish is impregnated into a substrate and laminated to form a laminate. You can get a board.

Examples of the phosphorus-containing compound used in the present invention include those represented by the above chemical structural formula (1). In this case, the raw material containing the epoxide compound, the phosphorus-containing compound and (meth) acrylic acid is used. The reactivity of the formation reaction of the phosphorus-containing compound can be improved, and a phosphorus-containing vinyl ester can be easily produced. Here, examples of the structure of the functional group represented by R1 in the formula include those represented by the chemical structural formula group shown in the following [Chemical formula 7].

[0035]

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These phosphorus-containing compounds can be obtained by a reaction between phosphine oxide and benzoquinone or a reaction between phosphine oxide and a polyfunctional phenol having an allyl group.

Here, as the phosphorus-containing compound, the phosphorus-containing compound (10- (2,2)
5-dihydroxyphenyl) -10H-9-oxa-1
0-phosphaphenanthrene-10-oxide) and a phosphorus-containing compound (9,1) represented by the above chemical structural formula (3).
0-dihydro-9oxa-10-phosphaphenanthrene-10-oxide).

As the epoxide compound (hereinafter, also referred to as polyepoxide compound), any of saturated or unsaturated compounds can be used, and aliphatic, alicyclic, aromatic, heterocyclic, etc. compounds can be used. be able to. Furthermore, these epoxide compounds may contain substituents which do not cause disturbing side reactions under mixing or reaction conditions, such as alkyl or aryl substituents, ether groups and the like.
In addition to using one type of epoxide compound, a mixture of two or more types of epoxide compounds may be used. As these polyepoxide compounds,
Although those having an average molecular weight Mn of up to about 9000 can be used, those having a range of about 150 to 4000 are generally used.

These polyepoxide compounds include, for example, polyhydric, preferably dihydric alcohols, phenols, hydrogenation products of these phenols and / or novolaks (mono- or polyhydric phenols in the presence of an acidic catalyst). Phenols and / or cresols with aldehydes, preferably formaldehyde)
Which are obtained by known methods, for example, by reacting a polyol with epichlorohydrin.

Examples of suitable polyhydric phenols include resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), an isomer mixture of dihydroxydiphenylmethane (bisphenol F), 4,4'- Dihydroxydiphenylcyclohexane, 4,4′-dihydroxy-3,3′-dimethyldiphenylpropane, 4,4′-dihydroxybiphenyl,
4,4'-dihydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) ethane, 1,1'-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxytert-butylphenyl) propane , Bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, tris (4-hydroxyphenyl) methane and 1,1'-bis (4-hydroxyphenyl) ether.

Polyglycidyl ethers of polyhydric aliphatic alcohols are also suitable as polyepoxide compounds. Preferred examples of such polyhydric alcohols include 1,4-butanediol, 1,6-hexanediol, polyalkylene glycol, glycerol, trimethylolpropane, 2,2-bis (4-hydroxycyclohexyl) propane, and pentaerythritol It is.

Other suitable polyepoxide compounds are
(Poly) glycidyl esters, which convert epichlorohydrin or similar epoxide compounds into aliphatic, cycloaliphatic or aromatic polycarboxylic acids such as oxalic acid, adipic acid, glutaric acid, phthalic acid, isophthalic acid, It is obtained by reacting terephthalic acid, tetrahydrophthalic acid or hexahydrophthalic acid, 2,6-naphthalenedicarboxylic acid and dimerized fatty acids. These examples are
Diglycidyl terephthalate and diglycidyl hexahydrophthalate.

Other examples of polyepoxide compounds which can be used are those based on heterocyclic systems,
For example, hydantoin epoxy resin, triglycidyl isocyanurate and / or oligomer thereof, triglycidyl-p-aminophenol, triglycidyl-p-aminodiphenylether, tetraglycidyldiaminodiphenylmethane, tetraglycidyldiaminodiphenylether, tetrakis (4 ­ glycidyloxyphenyl) ethane , Urazole epoxide, uracil epoxide, and oxazolidinone-modified epoxy resin. Other polyepoxides are aromatic amines, such as aniline,
For example, those based on N, N-diglycidylaniline, diaminodiphenylmethane and N, N'-dimethylaminodiphenylmethane or N, N'-dimethylaminodiphenylsulfone. Other suitable polyepoxide compounds are Henry Lee and Kris
"Handbook of Ep" by Neville
oxy Resins ", McGraw-Hill B
book Company, 1967, Henry Le
e "Epoxy Resins", Amer
ican Chemical Society, 197
0, Wagner / Sarx, "Lackkunsth
arze ", Carl Hanser Verlag (1
971), 5th edition, 174 f
f. "Angew. Makromol. Chemi.
e ", Vol. 44 (1975), pages 151.
to 163, DE-A 27 57 733
Specification and EP-A-0 384 939
It is described in the specification.

In the present invention, the reaction of the epoxide compound, the phosphorus-containing compound and the (meth) acrylic acid as described above is performed simultaneously in producing the phosphorus-containing vinyl ester. Simultaneously performing the reaction means that the epoxide compound, the phosphorus-containing compound and the (meth) acrylic acid are mixed without proceeding the reaction between the components to prepare a reactive mixture, and the reaction mixture is added to the reactive mixture. This means that, after setting up a reaction system in which these three types of raw material components are mixed, the formation reaction of the phosphorus-containing vinyl ester in the reaction system is started. The reaction for producing the phosphorus-containing vinyl ester can be started by adding a catalyst such as triphenylphosphine to a reactive mixture in which three kinds of raw material components are mixed.

A specific example of a method for preparing a phosphorus-containing vinyl ester will be described. The amounts of the various components shown below, and the values of the temperature, time, and acid value described in parentheses show one of the specific examples, and the amounts of these components are as follows. Not limited.

First, a phosphorus-containing compound (10- (2,5-dihydroxyphenyl) -10H) was placed in a four-necked flask having an appropriate volume in which a condenser, a stirrer, and a thermometer were set.
-9-oxa-10-phosphaphenanthrene-10-
Oxide; manufactured by Sanko Co., Ltd .; "HCA-HQ") 88.
2 g and 177.5 g of an epoxide compound (manufactured by Yuka Shell Epoxy Co., Ltd .; "Epicoat 152") are mixed, and further diluted with 100 g of styrene as a solvent.

The mixture is heated without initiating the reaction, and the temperature at which the viscosity of the mixture is sufficiently low (about 70 ° C.)
When this is reached, 52.7 g of methacrylic acid are incorporated into this mixture to prepare a reactive mixture in the flask.

Next, 0.25 g of hydroquinone was added to the reaction mixture, and the reaction mixture was further heated. When the temperature reached a homogeneous solution (about 100 ° C.), triphenylphosphine was added as a catalyst. Add .53 g to initiate the phosphorus-containing vinyl ester formation reaction.

In this state, the reaction proceeds while measuring and tracking the acid value of the solution in the flask as needed.
After the reaction heat is generated by the reaction due to the addition of the catalyst, after a lapse of the heat (about 3 hours), 0.32 g of triphenylphosphine is added as an additional catalyst, and 120.6 g of styrene is added as an additional solvent. Add.

The reason why the catalyst is added in two portions is as follows.
This is to prevent excessive heat of reaction from being generated due to rapid progress of the reaction, and the solvent is added in two portions. When the entire amount of the solvent is added at once, the dilution effect significantly reduces the reaction rate. This is because it takes a long time to complete the reaction.

Using the acid value of the solution in the flask as an evaluation criterion, the point at which methacrylic acid has reacted to an extent sufficient for the product to have radical polymerizability (the oxidation was reduced to 15 or less) At time), the flask is cooled assuming that the reaction for producing the phosphorus-containing vinyl ester has been completed. At this time, the phosphorus-containing vinyl ester is produced in the flask. At this time, the time from the start to the end of the reaction is about 8 hours.

Further, from a reactive mixture of two or more epoxide compounds having different compositions, a phosphorus-containing compound and (meth) acrylic acid, a phosphorus-containing vinyl ester is separately produced, and the two or more separately produced vinyl esters are produced. Can be mixed.

Here, the hydroquinone used in the process of producing the above-mentioned phosphorus-containing vinyl ester is compounded as a polymerization inhibitor and absorbs radicals in the reactive mixture during the reaction and the product obtained after the reaction. This prevents the polymerizable double bond in the phosphorus-containing vinyl ester from undergoing self-polymerization and the reaction from running away.

In producing the phosphorus-containing vinyl ester in this manner, in order to sufficiently improve the flame retardancy of the phosphorus-containing vinyl ester and the radically polymerizable resin composition prepared using the phosphorus-containing vinyl ester, It is preferable to use 8 to 75 parts by mass of the phosphorus-containing compound based on 100 parts by weight of the total amount of the epoxide compound, the phosphorus-containing compound and the (meth) acrylic acid as the raw materials. If the amount of the phosphorus-containing compound is less than this range, it is difficult to sufficiently improve the flame retardancy. Conversely, if the amount of the phosphorus compound exceeds this range, the reaction point (epoxy group) in the epoxide compound is occupied by the phosphorus compound, and there is little room for the epoxide compound to react with (meth) acrylic acid. As a result, the concentration of the radical polymerizable double bond in the product is reduced. For this reason, it is difficult to form a sufficient three-dimensional cross-linked structure even when the cured product is formed by radical polymerization of the product, and a radical polymerizable resin that exhibits sufficient curability using such a product is obtained. It becomes difficult to prepare the composition.

In order to sufficiently improve the flame retardancy,
The novolak-type epoxy resin is used as an epoxide compound in an amount of 10 to 100 parts by weight of the total amount of the epoxide compound, phosphorus-containing compound and (meth) acrylic acid as raw materials.
It is also preferable to use 60 parts by mass. If the used amount of the novolak type epoxy resin is less than this range, it is difficult to sufficiently improve the flame retardancy, and if the used amount exceeds this range, the laminated board using the radical polymerizable resin composition is used. In the case of manufacturing, the adhesiveness of the laminate may be reduced.

Here, the total amount used means the total amount of each component used to obtain the phosphorus-containing vinyl ester. In obtaining the phosphorus-containing vinyl ester, two or more reactive mixtures are used. When two or more kinds of separately containing phosphorus-containing vinyl esters are mixed, it means the total amount of the components used in the two or more kinds of reactive mixtures used to obtain the mixed phosphorus-containing vinyl esters. .

The thus obtained phosphorus-containing vinyl ester is further blended with a radically polymerizable monomer such as styrene or diallyl phthalate, a radical polymerization initiator, and other fillers, if necessary, to form a radically polymerizable resin composition. This radical polymerizable resin composition does not need to contain a halogen such as bromine or chlorine, and has high flame retardancy. At this time, the radical polymerizable resin composition contains at least one of a metal hydroxide, a phosphate ester, and a substance having three or more radical polymerizable double bonds in one molecule. By doing so, the flame retardancy can be further improved.

Here, when the phosphorus-containing vinyl ester is prepared as a styrene solution as described above, this styrene can be used as it is as the radical polymerizable monomer of the radical polymerizable resin composition.

When compounding a metal hydroxide, for example, aluminum hydroxide, magnesium hydroxide and the like can be used.

The mixing amount of the metal hydroxide is preferably 30 to 465 parts by mass based on 100 parts by mass of the phosphorus-containing vinyl ester in the radically polymerizable resin composition. If the compounding amount of the metal hydroxide is less than this range, it is difficult to sufficiently obtain the effect of flame retardancy, and if the compounding amount exceeds this range, using the radical polymerizable resin composition There is a possibility that the workability and heat resistance of the manufactured laminate will be reduced.

When a phosphate ester is blended, a condensed aromatic phosphate ester, triphenyl phosphate,
A material selected from cresyl di 2,6-xylenyl phosphate can be used. Here, as the aromatic condensed phosphoric acid ester, 1,3-phenylenebis (dixylenylphosphate), 1,3-phenylenebis (diphenylphosphate), 2-propylidene-di-4,4′-
1,3-phenylenebis (diphenyl phosphate),
2-propylidene-di-4,4'-1,3-phenylenebis (dicresyl phosphate) or the like can be used.

The amount of the phosphoric acid ester is preferably 5 to 40 parts by mass based on 100 parts by mass of the phosphorus-containing vinyl ester in the radically polymerizable resin composition. If the amount of the phosphate ester is less than this range, it is difficult to obtain a sufficient flame-retardant effect, and if the amount exceeds this range, the radical polymerizable resin composition is used. There is a possibility that the moisture resistance and heat resistance of the laminated board manufactured by the above method may be reduced.

When a substance having three or more radically polymerizable double bonds in one molecule is blended, heat resistance can be improved. In this case, it is preferable to use a substance having a structure represented by the following chemical structural formula (4) or (5) in the molecule because flame retardancy is not impaired. Examples of the substance having a structure represented by the following chemical structural formula (4) or (5) in such a molecule include triallyallyl isocyanurate, triallyl cyanurate, triallyl isocyanurate, triacryl formal, and ethoxy. Isocyanuric acid triacrylate (CA40220-08-4)
And the like.

[0064]

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As a substance having three or more double bonds in one molecule other than the above, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate and the like can be used.

In one molecule, three or more radically polymerizable
The compounding amount of the substance having a heavy bond is preferably 5 to 105 parts by mass based on 100 parts by mass of the phosphorus-containing vinyl ester in the radically polymerizable resin composition. 3 in one molecule
If the amount of the substance having one or more radical polymerizable double bonds is less than this range, the heat resistance may be reduced. Conversely, if the amount exceeds this range, the radical polymerizable resin composition The crosslink density of the cured product becomes too high, and the laminate produced using the radically polymerizable resin composition may become brittle.

The above-mentioned radical polymerizable resin composition can be used to produce a laminate by a continuous method. That is, in FIG. 1 described above, a long glass woven cloth (glass cloth) 1a is passed through the resin impregnation tank 2a to which the radical polymerizable resin composition has been supplied.
The glass woven fabric 1a is impregnated with the radically polymerizable resin composition, and the resin impregnated layer 2b to which the radically polymerizable resin composition is supplied is a long glass nonwoven fabric (glass paper).
1b, the glass nonwoven fabric 1b is impregnated with the radically polymerizable resin composition. Next, while continuously feeding, the glass nonwoven fabric 1b is put inside and the glass woven fabric 1a is put on the front side, and the sheets are passed through the rolls 3 and further, a long metal foil 4 such as a copper foil is sent continuously. , Glass woven cloth 1
a, the sheet is passed through a roll 3 and is successively passed through a heat-curing furnace 5 to be heat-cured, and then cut by a cutting device 6, whereby a CEM-3 type composite laminate A is cut. It can be manufactured.

[0068]

Next, the present invention will be described specifically with reference to examples.

(Examples 1 to 14, Comparative Examples 1 and 2) Resin compositions used in Examples and Comparative Examples were prepared according to the formulations shown in Table 1. The details are shown below.

Example 1 A 3 L flask equipped with a cooling tube, a stirrer, and a thermometer was charged with the chemical structural formula (2).
A phosphorus compound represented by the formula (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, "HCA" manufactured by Sanko Corporation
-HQ ") and 342 g of a bisphenol F type epoxy resin (" YDF-170 "manufactured by Toto Kasei) were added, and 189 g of styrene was further added.

The mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture became sufficiently low, 95 g of methacrylic acid was blended into the mixture to prepare a reactive mixture in a flask. did.

Next, 0.2 g of hydroquinone was added to the reaction mixture, and the reaction mixture was further heated.
g was added to initiate the phosphorus-containing vinyl ester formation reaction.

In this state, the reaction was allowed to proceed while measuring and tracking the acid value of the solution in the flask as needed.
After 3 hours, 0.6 g of triphenylphosphine and 68 g of styrene were added.

When the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature, and a styrene solution of a phosphorus-containing vinyl ester was obtained in the flask.

After further adding 257 g of aluminum hydroxide and 257 g of magnesium hydroxide to the flask and stirring the mixture well, a radical initiator (manufactured by NOF CORPORATION,
11 g of "Park Mill H80") was added to obtain a radically polymerizable resin composition.

(Example 2) A 3 L flask equipped with a cooling tube, a stirrer, and a thermometer was charged with the chemical structural formula (2)
A phosphorus compound represented by the formula (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, "HCA" manufactured by Sanko Corporation
-HQ ") and 380 g of a bisphenol A type epoxy resin (" YD-128 ", manufactured by Toto Kasei) were added, and 201 g of styrene was further added.

This mixture is heated without starting the reaction, and when the temperature of the mixture reaches 70 ° C. and the viscosity of the mixture becomes sufficiently low, 95 g of methacrylic acid is blended into the mixture to prepare a reactive mixture in a flask. did.

Next, 0.2 g of hydroquinone was added to the reaction mixture, and the reaction mixture was further heated. When the temperature reached 100 ° C., triphenylphosphine 1
g was added to initiate the phosphorus-containing vinyl ester formation reaction.

In this state, the reaction was allowed to proceed while measuring and tracking the acid value of the solution in the flask as needed.
After 3 hours, 0.6 g of triphenylphosphine and 72 g of styrene were added.

When the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature to obtain a styrene solution of a phosphorus-containing vinyl ester in the flask.

Further, 273 g of aluminum hydroxide and 273 g of magnesium hydroxide were added to the flask and stirred well, and then a radical initiator (manufactured by NOF Corporation)
11 g of "Park Mill H80") was added to obtain a radically polymerizable resin composition.

Example 3 A 3 L flask equipped with a cooling pipe, a stirrer, and a thermometer was charged with the chemical structural formula (2).
A phosphorus compound represented by the formula (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, "HCA" manufactured by Sanko Corporation
-HQ ") and 684 g of bisphenol F type epoxy resin (" YDF-170 ", manufactured by Toto Kasei) were added, and 195 g of styrene was further added.

The mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture was sufficiently low, 259 g of methacrylic acid was added to the mixture.
A reactive mixture was prepared in the flask.

Next, 0.3 g of hydroquinone was added to the reactive mixture, and the reactive mixture was further heated, and when the temperature reached 100 ° C., 1.0 g of triphenylphosphine was added, and the phosphorus-containing vinyl ester was added. Was started.

In this state, the reaction proceeds while measuring and tracking the acid value of the solution in the flask as needed.
After 3 hours, 1.1 g of triphenylphosphine and 173 g of styrene were added.

When the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature to obtain a styrene solution of a phosphorus-containing vinyl ester in the flask.

After further adding 2508 g of aluminum hydroxide to the flask and stirring well, 18 g of a radical initiator (“Park Mill H80” manufactured by NOF Corporation) was added.
By addition, a radical polymerizable resin composition was obtained.

Example 4 A 3 L flask equipped with a cooling pipe, a stirrer, and a thermometer was charged with the chemical structural formula (2).
A phosphorus compound represented by the formula (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, "HCA" manufactured by Sanko Corporation
-HQ "), 342 g of bisphenol F type epoxy resin (manufactured by Toto Kasei," YDF-170 ") and bisphenol A type epoxy resin (manufactured by Toto Kasei," YD-
128 ") and 190 g of styrene and 154
g was added.

This mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture became sufficiently low, 181 g of methacrylic acid was added to the mixture.
A reactive mixture was prepared in the flask.

Next, 0.2 g of hydroquinone was added to the reactive mixture, and the reactive mixture was further heated. When the temperature reached 100 ° C., 1.0 g of triphenylphosphine was added, and the phosphorus-containing vinyl ester was added. Was started.

In this state, the reaction was allowed to proceed while measuring and following the acid value of the solution in the flask as needed.
After 3 hours, 0.9 g of triphenylphosphine and 138 g of styrene were added.

When the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature to obtain a styrene solution of a phosphorus-containing vinyl ester in the flask.

Further, 935 g of magnesium hydroxide was added to the flask, and the mixture was thoroughly stirred. Then, 15 g of a radical initiator (“Parkmill H80” manufactured by NOF Corporation) was added to obtain a radically polymerizable resin composition. Was.

(Example 5) A 3 L flask equipped with a cooling tube, a stirrer, and a thermometer was charged with the chemical structural formula (2).
A phosphorus compound represented by the formula (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, "HCA" manufactured by Sanko Corporation
-HQ ") 162 g, and phenol novolak type epoxy resin (manufactured by Toto Kasei," TDPN-638P ") 181
g, and 107 g of styrene was further added.

This mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture became sufficiently low, 284 g of methacrylic acid was added to the mixture.
A reactive mixture was prepared in the flask.

Next, 0.3 g of hydroquinone was added to the reactive mixture, and the reactive mixture was further heated, and when the temperature reached 100 ° C., 1.0 g of triphenylphosphine was added to the phosphorus-containing vinyl ester. Was started.

In this state, the reaction was allowed to proceed while measuring and tracking the acid value of the solution in the flask as needed.
After 3 hours, 1.1 g of triphenylphosphine and 94 g of styrene were added.

When the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature, and a styrene solution of a phosphorus-containing vinyl ester was obtained in the flask.

Further, 4761 g of aluminum hydroxide was added to the flask, and the mixture was thoroughly stirred. Then, 17 g of a radical initiator (“Park Mill H80” manufactured by NOF Corporation) was added.
By addition, a radical polymerizable resin composition was obtained.

(Example 6) In a flask having a capacity of 3 L in which a cooling tube, a stirrer, and a thermometer were set, the chemical structural formula (2)
A phosphorus compound represented by the formula (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, "HCA" manufactured by Sanko Corporation
-HQ ") 162 g, bisphenol F-type epoxy resin (Toyto Kasei," YDF-170 ") 513 g, and cresol novolak-type epoxy resin (Toto Kasei," YD-YD-170 ")
CN-704P "), and 299 g of styrene were further added.

This mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture became sufficiently low, 271 g of methacrylic acid was added to the mixture.
A reactive mixture was prepared in the flask.

Next, 0.4 g of hydroquinone was added to the reactive mixture, and the reactive mixture was further heated. When the temperature reached 100 ° C., 1.0 g of triphenylphosphine was added, and the phosphorus-containing vinyl ester was added. Was started.

In this state, the acid value of the solution in the flask was measured as needed, and the reaction was allowed to proceed while tracking the reaction.
After 3 hours, 1.2 g of triphenylphosphine and 475 g of styrene were added.

When the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature to obtain a styrene solution of a phosphorus-containing vinyl ester in the flask.

Further, 387 g of aluminum hydroxide was added to the flask, and the mixture was sufficiently stirred. Then, 24 g of a radical initiator (“Parkmill H80” manufactured by NOF Corporation) was added to obtain a radically polymerizable resin composition. Was.

Example 7 A 3 L flask equipped with a cooling pipe, a stirrer, and a thermometer was charged with the chemical structural formula (2).
A phosphorus compound represented by the formula (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, "HCA" manufactured by Sanko Corporation
-HQ ") and 684 g of bisphenol F type epoxy resin (" YDF-170 "manufactured by Toto Kasei) were mixed, and 189 g of styrene was further added.

This mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture became sufficiently low, 227 g of acrylic acid was blended into the mixture to prepare a reactive mixture in a flask. did.

Next, 0.3 g of hydroquinone was added to the reactive mixture, and the reactive mixture was further heated, and when the temperature reached 100 ° C., 1.0 g of triphenylphosphine was added, and the phosphorus-containing vinyl ester was added. Was started.

In this state, the reaction was allowed to proceed while measuring and following the acid value of the solution in the flask as needed.
After 3 hours, 0.8 g of triphenylphosphine and 169 g of styrene were added.

Then, when the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature, and a styrene solution of a phosphorus-containing vinyl ester was obtained in the flask.

After further adding 1863 g of magnesium hydroxide to the flask and stirring the mixture, 18 g of a radical initiator (“Park Mill H80” manufactured by NOF Corporation) was added.
By addition, a radical polymerizable resin composition was obtained.

Example 8 A 3 L flask equipped with a cooling tube, a stirrer, and a thermometer was charged with the chemical structural formula (2)
A phosphorus compound represented by the formula (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, "HCA" manufactured by Sanko Corporation
-HQ ") and 676 g of a bisphenol F type epoxy resin (" YDF-170 "manufactured by Toto Kasei) were added, and 200 g of styrene was further added.

This mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture became sufficiently low, 270 g of methacrylic acid was added to the mixture.
A reactive mixture was prepared in the flask.

Next, 0.5 g of hydroquinone was added to the reactive mixture, and the reactive mixture was further heated. When the temperature reached 100 ° C., 1.0 g of triphenylphosphine was added, and the phosphorus-containing vinyl ester was added. Was started.

In this state, the reaction was allowed to proceed while measuring and following the acid value of the solution in the flask as needed.
After 3 hours, 1.0 g of triphenylphosphine was added and 170 g of styrene were added.

Then, when the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature to obtain a styrene solution of a phosphorus-containing vinyl ester in the flask.

Further, a phosphorus compound (9, 10) represented by the chemical structural formula (3) was placed in a flask having a capacity of 3 L separately from the above.
-Dihydro-9oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Corporation, "HCA")
82 g and 170 g of a phenol novolak type epoxy resin ("YDPN-638P" manufactured by Toto Kasei) were mixed, and 101 g of styrene was further added.

The mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture became sufficiently low, 48 g of methacrylic acid was blended into the mixture to prepare a reactive mixture in a flask. did.

Next, 0.4 g of hydroquinone was added to the reactive mixture, and the reactive mixture was further heated. When the temperature reached 100 ° C., 0.3 g of triphenylphosphine was added, and the phosphorus-containing vinyl ester was added. Was started.

In this state, the reaction was allowed to proceed while measuring and tracking the acid value of the solution in the flask as needed.
After 3 hours, 0.3 g of triphenylphosphine and 61 g of styrene were added.

When the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature to obtain a styrene solution of a phosphorus-containing vinyl ester in the flask.

The styrene solutions of the two kinds of phosphorus-containing vinyl esters obtained as described above were mixed, and the mixture was further mixed with a phosphate ester (cresyl 2,6-xylenyl phosphate, “PX-110” manufactured by Daihachi Chemical Co., Ltd.). ) And 1623 g of aluminum hydroxide, and after stirring well, a radical initiator ("Park Mill H8, manufactured by NOF Corporation")
0 ") was added to obtain a radically polymerizable resin composition.

Example 9 A 3 L flask equipped with a cooling pipe, a stirrer, and a thermometer was charged with the chemical structural formula (2).
A phosphorus compound represented by the formula (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, "HCA" manufactured by Sanko Corporation
-HQ ") 162 g and phenol novolak type epoxy resin (" YDPN-638P ", manufactured by Toto Kasei) 729
g, bisphenol A type epoxy resin (Toto Kasei,
381 g of “YD-128”), and 547 g of styrene was further added.

This mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture became sufficiently low, 460 g of methacrylic acid was added to the mixture.
A reactive mixture was prepared in the flask.

Next, 1.2 g of hydroquinone was added to the reactive mixture, and the reaction mixture was further heated, and when the temperature reached 100 ° C., 1.5 g of triphenylphosphine was added to obtain a phosphorus-containing vinyl ester. Was started.

In this state, the reaction was allowed to proceed while measuring and tracking the acid value of the solution in the flask as needed.
After 3 hours, 2.0 g of triphenylphosphine and 332 g of styrene were added.

Then, when the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature to obtain a styrene solution of a phosphorus-containing vinyl ester in the flask.

Further, 101 g of a phosphoric acid ester (cresyl 2,6-xylenyl phosphate, “PX-110” manufactured by Daihachi Chemical Co., Ltd.) and 4323 g of aluminum hydroxide were added to the flask, and the mixture was stirred well. 2 radical initiators (Nippon Yushi Co., Ltd., “Park Mill H80”)
By adding 8 g, a radically polymerizable resin composition was obtained.

Example 10 A phosphorus compound represented by the chemical structural formula (3) (9,10-dihydro-9) was placed in a 3 L flask equipped with a cooling tube, a stirrer, and a thermometer.
259 g of oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., “HCA”) and a phenol novolak type epoxy resin (manufactured by Toto Kasei, “Y
DPN-638P ") and 302 g of styrene.

This mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture became sufficiently low, 155 g of methacrylic acid was added to the mixture.
A reactive mixture was prepared in the flask.

Next, 0.7 g of hydroquinone was added to the reaction mixture, and the reaction mixture was further heated. When the temperature reached 100 ° C., 1.6 g of triphenylphosphine was added to the reaction mixture. Was started.

In this state, the reaction was allowed to proceed while measuring and following the acid value of the solution in the flask as needed.
After 3 hours, 1.0 g of triphenylphosphine was added and 213 g of styrene were added.

Then, when the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature, and a styrene solution of a phosphorus-containing vinyl ester was obtained in the flask.

Further, 300 g of a phosphoric acid ester (cresyl 2,6-xylenyl phosphate, “PX-110” manufactured by Daihachi Chemical Co., Ltd.) and 3545 g of aluminum hydroxide were added to the flask, and the mixture was stirred well. 1 radical initiator ("Park Mill H80" manufactured by NOF Corporation)
By adding 8 g, a radically polymerizable resin composition was obtained.

(Example 11) A phosphorus compound (9,10-dihydro-9) represented by the chemical structural formula (3) was placed in a flask having a capacity of 3 L in which a cooling tube, a stirrer, and a thermometer were set.
173 g of oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., "HCA") and a phenol novolak type epoxy resin (manufactured by Toto Kasei, "Y
DPN-638P ") and 228 g of styrene.

This mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture became sufficiently low, 103 g of methacrylic acid was added to the mixture.
A reactive mixture was prepared in the flask.

Next, 0.5 g of hydroquinone was added to the reactive mixture, and the reactive mixture was further heated, and when the temperature reached 100 ° C., 1.1 g of triphenylphosphine was added to obtain a phosphorus-containing vinyl ester. Was started.

In this state, the reaction was allowed to proceed while measuring and following the acid value of the solution in the flask as needed.
After 3 hours, 0.6 g of triphenylphosphine was added and 116 g of styrene were added.

Then, when the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature, and a styrene solution of a phosphorus-containing vinyl ester was obtained in the flask.

Further, 230 g of a phosphoric acid ester (cresyl 2,6-xylenyl phosphate, “PX-110” manufactured by Daihachi Chemical Co., Ltd.) and 2613 g of aluminum hydroxide were added to the flask, and the mixture was stirred well. 2 radical initiators (Nippon Yushi Co., Ltd., “Park Mill H80”)
By adding 0 g, a radically polymerizable resin composition was obtained.

(Example 12) A phosphorus compound (9,10-dihydro-9) represented by the chemical structural formula (3) was placed in a 3 L flask equipped with a cooling tube, a stirrer, and a thermometer.
173 g of oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., "HCA") and a phenol novolak type epoxy resin (manufactured by Toto Kasei, "Y
DPN-638P ") and 218 g of styrene.

The mixture was heated without initiating the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture was sufficiently low, 103 g of methacrylic acid was added to the mixture.
A reactive mixture was prepared in the flask.

Next, 0.5 g of hydroquinone was added to the reactive mixture, and the reactive mixture was further heated. When the temperature reached 100 ° C., 1.1 g of triphenylphosphine was added, and the phosphorus-containing vinyl ester was added. Was started.

In this state, the reaction was allowed to proceed while measuring and tracking the acid value of the solution in the flask as needed.
After 3 hours, 0.6 g of triphenylphosphine and 126 g of styrene were added.

When the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature to obtain a styrene solution of a phosphorus-containing vinyl ester in the flask.

In the flask, 230 g of a phosphoric acid ester (cresyl 2,6-xylenyl phosphate, “PX-110” manufactured by Daihachi Chemical Co., Ltd.), 52 g of triallyl isocyanurate, and 1769 of aluminum hydroxide were further added.
After adding g and stirring well, 13 g of a radical initiator (manufactured by NOF CORPORATION, “Park Mill H80”) was added,
A radically polymerizable resin composition was obtained.

Example 13 A phosphorus compound (9,10-dihydro-9) represented by the chemical structural formula (3) was placed in a flask having a capacity of 3 L in which a cooling tube, a stirrer, and a thermometer were set.
173 g of oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., "HCA") and a phenol novolak type epoxy resin (manufactured by Toto Kasei, "Y
DPN-638P ") and 246 g of styrene.

The mixture was heated without starting the reaction, and when the temperature reached 70 ° C. and the viscosity of the mixture became sufficiently low, 103 g of methacrylic acid was added to the mixture.
A reactive mixture was prepared in the flask.

Next, 0.5 g of hydroquinone was added to the reactive mixture, and the reactive mixture was further heated. When the temperature reached 100 ° C., 1.1 g of triphenylphosphine was added, and the phosphorus-containing vinyl ester was added. Was started.

In this state, the reaction was allowed to proceed while measuring and tracking the acid value of the solution in the flask as needed.
After 3 hours, 0.6 g of triphenylphosphine and 98 g of styrene were added.

When the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature to obtain a styrene solution of a phosphorus-containing vinyl ester in the flask.

In this flask, 185 g of a phosphoric acid ester (cresyl 2,6-xylenyl phosphate, “PX-110” manufactured by Daihachi Chemical Co., Ltd.) and tetramethylolmethane trimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. T
MM360 ") 140 g and aluminum hydroxide 183
After adding 0 g and stirring well, 14 g of a radical initiator (manufactured by NOF Corporation, “Park Mill H80”) was added to obtain a radically polymerizable resin composition. (Example 14) A phosphorus compound (9,10-dihydro-9oxa-10-phosphaphenanthrene represented by the chemical structural formula (3) was placed in a 3 L capacity flask in which a cooling tube, a stirrer, and a thermometer were set. 216 g of -10-oxide (“HCA” manufactured by Sanko Co., Ltd.) and 380 g of bisphenol A type epoxy resin (“YD128” manufactured by Toto Kasei)
And 237 g of styrene were further added.

This mixture was heated without starting the reaction, and when the temperature of the mixture reached 70 ° C. and the viscosity of the mixture became sufficiently low, 86 g of methacrylic acid was blended into the mixture to prepare a reactive mixture in a flask. did.

Next, 0.3 g of hydroquinone was added to the reactive mixture, and the reaction mixture was further heated, and when the temperature reached 100 ° C., 1.2 g of triphenylphosphine was added to the phosphorus-containing vinyl ester. Was started.

In this state, the reaction was allowed to proceed while measuring and tracking the acid value of the solution in the flask as needed.
After 3 hours, 0.3 g of triphenylphosphine and 130 g of styrene were added.

Then, when the acid value of the solution in the flask became 15 or less, the flask was cooled to room temperature to obtain a styrene solution of a phosphorus-containing vinyl ester in the flask.

Further, 250 g of a phosphoric acid ester (cresyl 2,6-xylenyl phosphate, “PX-110” manufactured by Daihachi Chemical Co., Ltd.), 450 g of ethoxylated isocyanuric acid triacrylate, and 3148 g of aluminum hydroxide were placed in the flask. Was added and stirred well, and then 19 g of a radical initiator (manufactured by NOF CORPORATION, "Park Mill H80") was added to obtain a radically polymerizable resin composition.

(Comparative Example 1) Bisphenol A type epoxy resin (manufactured by Toto Kasei, "YD12") was placed in a 3 L flask.
8 ") 380 g, 0.2 g of hydroquinone, 189 g of methacrylic acid and 0.6 g of triphenylphosphine were added and reacted well at 120 ° C. until the acid value became 20 or less.

Further, 244 g of a styrene monomer, 244 g of aluminum hydroxide and 244 g of magnesium hydroxide were added, and the mixture was stirred well and cooled to room temperature, and 1 radical initiator (“Parkmill H80” manufactured by NOF Corporation) was added.
0 g was added to obtain a radically polymerizable resin composition.

Comparative Example 2 A 3 L flask was charged with a phosphorus compound (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10 represented by the chemical structural formula (2). -Oxide, 162 g of "HCA-HQ" manufactured by Sanko Co., Ltd., and 342 of bisphenol F type epoxy resin ("YDF-170" manufactured by Toto Kasei)
g and 1 g of triphenylphosphine, and the mixture was stirred at 148 ° C. for 1 hour to obtain a brownish transparent liquid.

After cooling the liquid to 120 ° C., 0.2 g of hydroquinone, 95 g of methacrylic acid and 0.6 g of triphenylphosphine were added and reacted well at 120 ° C. until the acid value became 20 or less. Further, after adding 257 g of styrene monomer, 257 g of aluminum hydroxide, and 257 g of magnesium hydroxide and stirring well,
After cooling to room temperature, 11 g of a radical initiator (manufactured by NOF CORPORATION, "Park Mill H80") was added to obtain a radically polymerizable resin composition. (Evaluation) The radical polymerizable resin composition obtained in each of the above Examples and Comparative Examples was subjected to an inner dimension of 100 mm × 150 mm × 2.
After the mixture was poured into a mold having a thickness of 110 mm and heated at 110 ° C. for 30 minutes, after-curing was performed at 180 ° C. for 30 minutes to obtain a plate-like cured product.

The resin composition before curing was applied to a plain woven glass cloth (thickness: 200 μm, size: 300 mm × 300 m).
m) and glass paper (single weight 51 g / m ² , density 0.
14 g / cm ³ , size 300 mm x 300 mm), two pieces of glass paper impregnated product were placed in the center, and one piece of plain woven glass cloth product was placed on each side to form a sandwich structure. One piece of foil was placed, and the laminate was sandwiched between metal plates, heated at 110 ° C. for 30 minutes, and after-cured at 180 ° C. for 30 minutes,
A copper-clad laminate having a thickness of 1.6 mm was obtained.

A test piece having a length of 125 mm and a width of 13 mm was cut out from the laminate and the plate-like cured product from which the copper foil of the laminate was removed by etching.

Underwriters Labora
Tories'"Test for Flammabil"
entity of Plastic Materials-
According to UL 94 ", a test of the combustion behavior was carried out on a test piece 125 mm long and 13 mm wide.

Table 1 shows the results of the evaluation.

Here, the values of the phosphorus-containing compound and the novolak-type epoxy resin in the column of the compounding ratio in the table are based on 100 parts by mass of the total amount of the epoxide compound, the phosphorus-containing compound and the (meth) acrylic acid of each component. The amounts of the metal hydroxide, the phosphoric acid ester and the substance having three or more radical double bonds in one molecule are shown in the following table.
Shows the amount used in parts by mass.

[0167]

[Table 1]

As is evident from Table 1, the test pieces obtained in the examples using the resin composition of the present invention had V-
Evaluations of 1 to V-0 could be obtained. In contrast, the test piece of Comparative Example 1 was completely burned.

Further, the test piece obtained in the example using the resin composition of the present invention had the same flame retardancy as the test piece of Comparative Example 2 in which a phosphorus-containing vinyl ester was produced by a two-step reaction. Evaluation was obtained.

[0170]

The method for producing a phosphorus-containing vinyl ester according to claim 1 of the present invention is a method for producing a phosphorus-containing vinyl ester by reacting a raw material containing an epoxide compound, a phosphorus-containing compound and (meth) acrylic acid. Since the reaction of the resin, the phosphorus-containing compound and the (meth) acrylic acid are performed simultaneously, it is possible to obtain a phosphorus-containing vinyl ester having good flame retardancy despite containing no halogen and further having excellent heat resistance. You can do it. Moreover, the production of the phosphorus-containing vinyl ester can be performed in a one-step reaction, and the phosphorus-containing vinyl ester can be easily produced from the epoxide compound, the phosphorus-containing compound and (meth) acrylic acid by a simple production process. It can be manufactured.

Further, according to the invention of claim 2, in addition to the constitution of claim 1, a raw material containing an epoxide compound, a phosphorus-containing compound and (meth) acrylic acid is mixed, and the reaction is started by adding a catalyst. The reaction of the compound, the phosphorus-containing compound and the (meth) acrylic acid can be performed simultaneously by the addition of a catalyst, and the production of the phosphorus-containing vinyl ester can be performed in a one-step reaction. A phosphorus-containing vinyl ester can be easily produced from the contained compound and (meth) acrylic acid by a simple production process.

The invention of claim 3 provides, in addition to the constitution of claim 1 or 2, the use of a phosphorus-containing compound represented by the above-mentioned chemical formula (1) as a phosphorus-containing compound. The reactivity of the production reaction of the phosphorus-containing compound from the raw material containing the phosphorus-containing compound and the (meth) acrylic acid can be improved, and the phosphorus-containing vinyl ester can be easily produced.

Further, the invention of claim 4 provides, in addition to the constitution of any one of claims 1 to 3, 8 to 75 parts by weight based on 100 parts by mass of the total amount of the epoxide compound, the phosphorus-containing compound and the (meth) acrylic acid. Since the phosphorus-containing compound is used in parts by mass, the flame retardancy of the phosphorus-containing vinyl ester can be further improved, and a radically polymerizable resin composition having good curability can be prepared using the phosphorus-containing vinyl ester. Is what you can do.

The invention according to claim 5 is characterized in that, in addition to the constitution of any one of claims 1 to 4, 10 to 60 parts by mass based on 100 parts by mass of the total amount of the epoxide compound, the phosphorus-containing compound and the (meth) acrylic acid. By using a novolak type epoxy resin in parts by mass, the flame retardancy of the phosphorus-containing vinyl ester can be further improved, and the laminated board can be formed with a radical polymerizable resin composition obtained using the phosphorus-containing vinyl ester. It is possible to obtain a laminate having good adhesion when forming.

[0175] The invention of claim 6 provides, in addition to the constitution of any one of claims 1 to 5, as a phosphorus-containing compound, a phosphorus-containing compound represented by the above chemical structural formula (2); Since at least one of the phosphorus-containing compounds represented by (3) is used, the reactivity of the production reaction of the phosphorus-containing compound from a raw material containing an epoxide compound, a phosphorus-containing compound, and (meth) acrylic acid is improved. And a phosphorus-containing vinyl ester can be easily produced.

The method for producing a radically polymerizable resin composition according to claim 7 of the present invention is characterized in that the phosphorus-containing vinyl ester obtained by the method according to any one of claims 1 to 6 is treated with metal water. Oxides, phosphates and 3 per molecule
Since at least one of the substances having two or more radical polymerizable double bonds is blended, it has good flame retardancy despite not containing halogen, and furthermore has excellent heat resistance. A radically polymerizable resin composition can be obtained. In addition, the production of the phosphorus-containing vinyl ester used for obtaining the radically polymerizable resin composition can be performed in a one-step reaction, and the epoxide compound, the phosphorus-containing compound and the (meth) acrylic acid The vinyl ester containing can be easily produced by a simple production process, and therefore, a radically polymerizable resin composition can be easily produced by a simple production process.

According to the invention of claim 8, in addition to the constitution of claim 7, 30 to 465 parts by mass of a metal hydroxide is blended with respect to 100 parts by mass of the phosphorus-containing vinyl ester. The flame retardancy of the product can be further improved, and a laminate having good workability and heat resistance can be obtained when the laminate is formed from the radically polymerizable resin composition.

According to a ninth aspect of the present invention, in addition to the constitution of the seventh or eighth aspect, a phosphoric acid ester of 5 to 40 parts by mass is blended with respect to 100 parts by mass of the phosphorus-containing vinyl ester. The flame retardancy of the composition can be further improved, and a laminate having good moisture resistance and heat resistance can be obtained when the laminate is formed from the radically polymerizable resin composition.

The invention of claim 10 is the invention of claims 7 to 9
In addition to any one of the above, the phosphorus-containing vinyl ester 1
Since 5 to 105 parts by mass of a substance having three or more radical polymerizable double bonds in one molecule per 100 parts by mass is added, the heat resistance of the radically polymerizable resin composition can be improved. In addition, it can prevent the crosslinked density of the cured product of the radical polymerizable resin composition from becoming too high, and can prevent the laminate manufactured using the radical polymerizable resin composition from becoming brittle. It is.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a manufacturing process of a laminate.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/521 C08K 5/521 C08L 55/00 C08L 55/00 (72) Inventor Hitoshi Kimura Kadoma, Osaka 1048 Oaza Kadoma Matsushita Electric Works Co., Ltd. (72) Inventor Yoshinori Uno 5-8 Nishomitabi-cho, Suita-shi, Osaka Japan Co., Ltd. 5-8 Nishiomibori-cho F-term in Nippon Shokubai Resin Research Institute Co., Ltd. (reference) 4J002 CD191 CD201 DE076 DE146 EW047 GF00 4J011 CA04 CB01 CB04 PA07 PA46 PB29 4J027 AE02 AE03 AE04 AE05 BA13 BA24 BA25 BA29 CA14 CA27 CC02 4J036 AA01A CC02 DD07 GA29 JA08

Claims (10)

[Claims] 1. A method for producing a phosphorus-containing vinyl ester in which a raw material containing an epoxide compound, a phosphorus-containing compound and (meth) acrylic acid is reacted, wherein the epoxy resin, the phosphorus-containing compound and (meth) acrylic acid are simultaneously reacted. A method for producing a phosphorus-containing vinyl ester, comprising: 2. A method for producing a phosphorus-containing vinyl ester according to claim 1, wherein raw materials containing an epoxide compound, a phosphorus-containing compound and (meth) acrylic acid are mixed and the reaction is started by adding a catalyst. . 3. The method for producing a phosphorus-containing vinyl ester according to claim 1, wherein a phosphorus-containing compound represented by the following chemical structural formula (1) is used as the phosphorus-containing compound. Embedded image 4. An amount of 8 per 100 parts by mass of the epoxide compound, the phosphorus-containing compound and the (meth) acrylic acid.
The method for producing a phosphorus-containing vinyl ester according to any one of claims 1 to 3, wherein the phosphorus-containing compound is used in an amount of from 75 to 75 parts by mass. 5. An amount of 1 to 100 parts by mass of the total amount of the epoxide compound, phosphorus-containing compound and (meth) acrylic acid.
The method for producing a phosphorus-containing vinyl ester according to any one of claims 1 to 4, wherein 0 to 60 parts by mass of a novolak epoxy resin is used. 6. The method of using at least one of a phosphorus-containing compound represented by the following chemical structural formula (2) and a phosphorus-containing compound represented by the following chemical structural formula (3): The method for producing a phosphorus-containing vinyl ester according to any one of claims 1 to 5, characterized in that: Embedded image Embedded image 7. A method according to claim 1, wherein the phosphorus-containing vinyl ester obtained by the method according to claim 1 is a metal hydroxide, a phosphate ester and three or more radically polymerizable compounds in one molecule. A method for producing a radically polymerizable resin composition, wherein at least one of the substances having a double bond is blended. 8. The method for producing a radically polymerizable resin composition according to claim 7, wherein 30 to 465 parts by mass of a metal hydroxide is added to 100 parts by mass of the phosphorus-containing vinyl ester. 9. The method for producing a radically polymerizable resin composition according to claim 7, wherein 5 to 40 parts by mass of a phosphoric acid ester is blended with respect to 100 parts by mass of the phosphorus-containing vinyl ester. 10. A compound having three or more radically polymerizable double bonds in one molecule in an amount of 5 to 105 parts by mass with respect to 100 parts by mass of the phosphorus-containing vinyl ester. 10. The method for producing a radically polymerizable resin composition according to any one of items 1 to 9.