JP2013060571A - Phosphorus-containing curing resin composition, and cured resin thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphorus-containing curing resin composition excellent in flame retardancy, electric properties and water absorption resistance, and containing a phosphorus atom in the resin skeleton, and a cured resin thereof.SOLUTION: There are provided: the phosphorus-containing curing resin composition containing at least one phosphorus-containing bisphenol compound represented by formula (1), at least one epoxy compound having two or more epoxy groups in the molecule, and at least one phenol resin having one or more phenolic hydroxyl groups in the molecule; and its cured resin. In the formula (1), R, R, Rand Rare each independently a specific substituent; p, q, r and s are each independently an integer of 0 to 4; and Ris a hydrogen atom, a specific alkyl group, an aryl group or the like.

Description

  The present invention relates to a phosphorus-containing curable resin composition and a cured resin product thereof. Specifically, a phosphorus-containing curable resin composition containing a phosphorus-containing bisphenol compound, an epoxy compound, a phenol resin, a curing accelerator, and the like, and a phosphorus-containing resin cured product in which a phosphorus atom formed by curing the phosphorus-containing curable resin composition is incorporated in a resin skeleton About.

  Epoxy resins, which are one of general-purpose resin cured products, are generally widely used in the fields of electrical and electronic materials, for example, materials for sealing electronic parts, materials for laminated plates, and the like. In particular, epoxy resin curable compositions for semiconductor encapsulation manufactured using phenol novolac resins and epoxy resins selected from the viewpoints of heat resistance and reliability are sufficient fires even at high temperatures from the viewpoint of safety. It is required to exhibit a preventive action, and its development has been actively conducted in recent years.

  By the way, various studies have already been conducted on methods for improving the flame retardancy of existing resins. For example, a flame retardant containing a halogen atom such as a resin composition to which a halogen compound is added or a resin using a monomer having a halogen atom is known to have good flame retardancy. Dioxins may be generated, and it was difficult to say that they were sufficiently satisfactory for human safety at high temperatures.

On the other hand, as a non-halogen flame retardant material made of a material that does not contain a halogen atom, a resin material to which an organic phosphorus compound is added has recently attracted attention. Although the resin material to which this organophosphorus compound is added has a high flame retardant effect compared to existing resins, depending on the compatibility of the material to be added, simply add the organophosphorus compound to the resin. -Mixing often causes so-called bleed-out phenomenon and does not show sufficient flame retardancy.
As means for solving such a problem, for example, Patent Document 1 discloses that a resin composition containing an oligomer in which a phosphate ester structure is incorporated in a skeleton exhibits an appropriate flame retardancy. Patent Document 2 discloses a flame-retardant epoxy resin in which a phosphorus atom is incorporated into a skeleton using 10-hydroxymethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as a raw material. Has been.

JP-A-11-343382 JP 2000-154234 A

However, the oligomer in the resin composition disclosed in Patent Document 1 is weak in hydrolysis resistance, and the cured resin produced from this resin composition has a water absorption property as a material for the electronic / electric field. I know it is expensive. Further, the compound described in Patent Document 2 also has a problem that satisfactory hydrolysis resistance cannot be obtained because it has a phosphoric acid bond moiety in the molecule.
From the above-mentioned prior art documents, various studies have been made on various resin materials from the viewpoint of flame retardancy so far, but the balance between good flame retardancy and other physical properties is still good. Development of flame retardant resin materials is required.

  Then, the subject of this invention is providing the phosphorus containing curable resin composition which was excellent in the flame retardance, the electrical property, and the water absorption resistance which contains a phosphorus atom in a resin frame | skeleton, and its resin cured material.

As a result of diligent study, the present inventors have solved the above problems with a phosphorus-containing curable resin composition containing a specific phosphorus-containing bisphenol compound, an epoxy compound, a phenol resin, and a curing initiator, and a cured resin product thereof. The present invention has been completed.
That is, this invention provides the following phosphorus containing curable resin composition and its resin hardened | cured material.

1. At least one phosphorus-containing bisphenol compound represented by the following general formula (1), at least one epoxy compound having two or more epoxy groups in one molecule, at least one molecule having one or more phenolic hydroxyl groups A phosphorus-containing curable resin composition comprising a phenol resin and at least one curing accelerator.

[In General Formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a fluorine atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. An oxy group, an aryl group having 6 to 18 carbon atoms which may have a substituent, or an aryloxy group having 6 to 18 carbon atoms which may have a substituent is shown. p, q, r, and s are each independently an integer of 0 to 4. R ⁵ is a hydrogen atom, a fluorine atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, or a carbon number. The C6-C12 aryl group which may have a C1-C6 alkyl group and a C1-C6 alkyloxy group is shown. ]

2. 2. The phosphorus-containing curable resin composition according to 1, wherein the epoxy compound having two or more epoxy groups in the molecule is at least one epoxy compound selected from the group consisting of a diepoxide compound, a triepoxide compound, and a polyepoxide compound. object.

3. A phenol resin having at least one phenolic hydroxyl group is a polycondensation product of phenols, bisphenols, naphthols and aldehydes, polycondensation products of phenols and dienes, and polycondensation of phenols and ketones. 3. The phosphorus-containing curable resin composition according to 1 or 2 above, which is at least one phenol resin selected from the group consisting of products.

4). The phosphorus containing resin hardened | cured material formed by hardening | curing the phosphorus containing curable resin composition as described in any one of said 1-3.

The phosphorus-containing curable resin composition of the present invention is a composition in which the cured product exhibits excellent flame retardancy, and is useful, for example, as a sealing material for electronic components in the electrical and electronic industries. is there.
In addition, the cured phosphorus-containing resin of the present invention using this also has excellent flame retardancy for use in a wide range of materials, for example, for the electrical and electronic industries, for sealing electronic components, for laminates, etc. It is useful as a cured product having Further, the phosphorus-containing curable resin composition of the present invention and a cured product using the same contain a phosphate bond in the molecule and other bonds that are cleaved by hydrolysis such as an ester bond and an amide bond. Therefore, good hydrolysis resistance is expected.

3 is a thermogravimetric analysis (TG-DTA) chart of the cured phosphorus-containing resin obtained in Example 1. FIG. 3 is a thermogravimetric analysis (TG-DTA) chart of the cured phosphorus-containing resin obtained in Example 2. FIG. It is a thermogravimetric analysis measurement (TG-DTA) chart of the cured epoxy resin obtained in Comparative Example 1. 4 is a thermogravimetric analysis (TG-DTA) chart of the cured phosphorus-containing resin obtained in Example 3. FIG. 4 is a thermogravimetric analysis (TG-DTA) chart of the cured phosphorus-containing resin obtained in Example 4. FIG. 6 is a thermogravimetric analysis (TG-DTA) chart of the cured phosphorus-containing resin obtained in Example 5. FIG. It is a thermogravimetric analysis measurement (TG-DTA) chart of the cured epoxy resin obtained in Comparative Example 2. It is a thermogravimetric analysis measurement (TG-DTA) chart of the phosphorus containing resin cured material obtained in Example 6. It is a thermogravimetric analysis measurement (TG-DTA) chart of the phosphorus containing resin cured material obtained in Example 7. 10 is a thermogravimetric analysis measurement (TG-DTA) chart of the cured phosphorus-containing resin obtained in Example 8. FIG. It is a thermogravimetric analysis measurement (TG-DTA) chart of the cured epoxy resin obtained in Comparative Example 3. 10 is a thermogravimetric analysis measurement (TG-DTA) chart of the cured phosphorus-containing resin obtained in Example 9. FIG. It is a thermogravimetric analysis measurement (TG-DTA) chart of the cured epoxy resin obtained in Comparative Example 4. It is a thermogravimetric analysis measurement (TG-DTA) chart of the phosphorus containing resin cured material obtained in Example 10. FIG. It is a thermogravimetric analysis measurement (TG-DTA) chart of the cured epoxy resin obtained in Comparative Example 5. 10 is a thermogravimetric analysis measurement (TG-DTA) chart of the cured phosphorus-containing resin obtained in Example 11. FIG. It is a thermogravimetric analysis measurement (TG-DTA) chart of the cured epoxy resin obtained in Comparative Example 6. It is a thermogravimetric analysis measurement (TG-DTA) chart of the phosphorus containing resin cured material obtained in Example 12. It is a thermogravimetric analysis measurement (TG-DTA) chart of the cured epoxy resin obtained in Comparative Example 7.

[Phosphorus-containing curable resin composition]
The phosphorus-containing curable resin composition of the present invention is a composition containing a specific phosphorus-containing bisphenol compound, an epoxy compound, a phenol resin, and a curing accelerator, and may further contain various additive compounds as necessary. It is.
The method for producing a phosphorus-containing curable resin composition of the present invention includes at least one phosphorus-containing bisphenol compound represented by the following general formula (1), at least one epoxy compound having two or more epoxy groups in the molecule, It can be obtained by a method in which at least one phenol resin having one or more phenolic hydroxyl groups in the molecule and at least one curing accelerator are mixed.

<Phosphorus-containing bisphenol compound>
The phosphorus-containing bisphenol compound of the present invention is represented by the following general formula (1).

In general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a fluorine atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkyloxy having 1 to 6 carbon atoms. A group, an aryl group having 6 to 18 carbon atoms which may have a substituent, or an aryloxy group having 6 to 18 carbon atoms which may have a substituent; p, q, r, and s are each independently an integer of 0 to 4. R ⁵ is a hydrogen atom, a fluorine atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, or a carbon number. The C6-C12 aryl group which may have a C1-C6 alkyl group and a C1-C6 alkyloxy group is shown.

  A C1-C6 alkyl group shows a linear, branched or cyclic aliphatic hydrocarbon group, and includes a positional isomer. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, t-butyl group, cyclobutyl group, n- Examples include a pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group.

  An alkyloxy group having 1 to 6 carbon atoms represents a group in which a linear, branched or cyclic aliphatic hydrocarbon group is bonded to an oxygen atom, and includes positional isomers. Specific examples of the alkyloxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropyloxy group, n-butoxy group, isobutyloxy group, t-butyloxy group, cyclo Examples include a butyloxy group, an n-pentyloxy group, a cyclopentyloxy group, an n-hexyloxy group, and a cyclohexyloxy group.

The aryl group having 6 to 18 carbon atoms which may have a substituent represents an aromatic hydrocarbon group which is unsubstituted or has a substituent, and more specifically, one or more aromatic hydrocarbon groups. The hydrogen atom may be substituted with, for example, an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms. Here, “alkyl group” and “alkyloxy group” have the same meanings as the alkyl group and alkyloxy group.
Specific examples of the aryl group include phenyl group, naphthyl group, anthranyl group, toluyl group, dimethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, cyclopropylphenyl group, n-butylphenyl group, Examples thereof include t-butylphenyl group, methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl group, isopropoxyphenyl group, cyclopropoxyphenyl group and n-butoxyphenyl group.

The aryloxy group having 6 to 18 carbon atoms which may have a substituent represents a group in which the aryl group is bonded to an oxygen atom, and further, one or more hydrogen atoms of the aryl group are, for example, a carbon number It may be substituted with 1 to 4 alkyloxy groups.
Specific examples of the aryloxy group include toluoyloxy group, dimethylphenyloxy group, ethylphenyloxy group, n-propylphenyloxy group, isopropylphenyloxy group, cyclopropylphenyloxy group, n-butylphenyloxy group, t -Butylphenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, n-propoxyphenyloxy group, isopropoxyphenyloxy group, cyclopropoxyphenyloxy group, n-butoxyphenyloxy group and the like.

From the above, in the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently preferably a nitro group, a cyano group, more preferably an alkyl group having 1 to 4 carbon atoms, and a carbon number of 1 -4 alkyloxy group and phenyl group, particularly preferably methyl group, ethyl group, methoxy group, ethoxy group and phenyl group.

p, q, r, and s are each independently an integer of 0 to 4, preferably 0 or 1, more preferably 0. When p, q, r, and s represent 0, it means unsubstituted. When p, q, r, and s represent an integer of 2 or more, the plurality of R ¹ , R ² , R ^3, and R ⁴ may be the same as or different from each other. Moreover, when several R < ¹ >, R < ² > is respectively substituted by the adjacent carbon atom in a benzene ring, you may couple | bond together and form a cyclic structure. R ¹ and R ² are preferably the same substituent.

For example, the phosphorus-containing bisphenol compound represented by the general formula (1) is a compound represented by the following formulas (2) to (4) according to the following reaction formula, for example, as in Reference Examples 1 to 3 described later. Although it can synthesize | combine by making it react, the synthesis | combining method in particular is not restrict | limited. In the following formulas (2) to (4), R ^{1 to} R ⁵ and p to s have the same meaning as described above.

Specifically, the diarylphosphine oxide compound represented by the above formula (2) and the hydroxyphenylalkylcarbonyl compound represented by the above formula (3) are reacted to form a phosphorus-containing aryl alcohol compound, and then the phosphorus-containing aryl. A phosphorus-containing bisphenol compound represented by the general formula (1) by reacting an alcohol compound with the phenol compound represented by the above formula (4) in the presence of an acid catalyst such as an inorganic acid, an organic sulfonic acid and an organic carboxylic acid. Can be synthesized. Moreover, in the presence of the same acid catalyst as described above, the compounds represented by the above formulas (2) to (4) can be simultaneously added and reacted.
In addition, the phosphorus containing bisphenol compound shown by the said General formula (1) which can be synthesize | combined by the said method may be used independently, or may use 2 or more types together.

<Epoxy compound>
The epoxy compound having two or more epoxy groups in the molecule contained in the phosphorus-containing curable resin composition of the present invention reacts with the phosphorus-containing bisphenol and the hydroxyl group of the phenol resin contained in the resin composition, resulting in a cured product. There is no particular limitation as long as it can be obtained.
From the above, the epoxy compound used is preferably (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether; 2,2-bis (4-glycidyloxyphenyl) propane 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, bisphenol F diglycidyl ether, 3,3 ′, 5,5′-tetramethyl- (1,1′-biphenyl) -4 , 4′-diol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and other diepoxide compounds; trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, tri (4-hydroxyphenyl) triepoxide compounds such as methane triglycidyl ether; epoxidized polybutadiene, cresol novolac polyglycidyl ether, polyepoxide compounds such as bisphenol A novolak polyglycidyl ether. In addition, the said epoxy compound may be used independently or may use 2 or more types together.

Further, among the above epoxy compounds, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexenylmethyl are more preferable. -3 ', 4'-epoxycyclohexene carboxylate, cresol novolac polyglycidyl ether, more preferably 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexenylmethyl-3', 4'- Epoxy cyclohexene carboxylate, cresol novolac polyglycidyl ether is used.
Moreover, as a commercial item of the epoxy compound which can be used in this invention, Mitsubishi Chemical's jER series (brand name), DIC's Epicron series (brand name), etc. are mentioned, for example.

<Phenolic resin>
Although there is no restriction | limiting in particular as a phenol resin which has one or more phenolic hydroxyl groups in the at least 1 sort (s) of molecule | numerator contained in the phosphorus containing curable resin composition of this invention, From a viewpoint of the moldability improvement as a resin material Therefore, the phenol resin having a softening point of 50 to 250 ° C., more preferably the phenol resin having a softening point of 50 to 200 ° C., and particularly preferably the phenol resin having a softening point of 50 to 150 ° C. is used. The phenol resin may be a liquid at room temperature (0 to 30 ° C.), for example. In addition, as a resin material of a cured resin obtained from the phosphorus-containing curable resin composition of the present invention, for example, for the purpose of improving the temporal stability against heat or external force, the hydroxyl value of the phenol resin used ( KOHmg / g) is preferably 10 to 1000, more preferably 30 to 500, and particularly preferably 50 to 500. In addition, the hydroxyl value uses the value computed according to the measuring method of JISK1557 or JISK0070.

Specific examples of the phenol resin include phenols (phenol, catechol, hydroquinone, resorcinol, alkyl-substituted phenol, aromatic-substituted phenol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, etc.), bisphenols (bisphenol A, bisphenol F, etc.), Or naphthols (α-naphthol, β-naphthol, alkyl-substituted naphthol, dihydroxynaphthalene, etc.) and aldehydes (formaldehyde, acetalded, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc. ) And polycondensates (such as novolac phenolic resins); phenols and dienes (terpenes) , Vinyl cyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.); phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone) , Benzophenone, etc.); and the phenols and / or modified products of the phenol resin. The said phenol resin may be used independently or may use 2 or more types together.
Moreover, as a commercial item of the phenol resin which can be used in this invention, Meiwa Kasei HF-1M (trade name), Meiwa Kasei MEH-7851 (trade name), Showa Denko BRG-556 (product) Name).

<Curing accelerator>
The curing accelerator contained in the phosphorus-containing curable resin composition of the present invention may be, for example, a photocuring accelerator or a thermosetting accelerator, and is not particularly limited, but preferably is an imidazole-based curing accelerator. An agent or a phosphorus curing accelerator is used. Moreover, although the specific example of the hardening accelerator is shown here, the hardening accelerator of this invention may be used independently, or may be used together 2 or more types.

(Imidazole curing accelerator)
Examples of the imidazole curing accelerator include imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyl. Imidazole, 1-cyanoethyl-2-undecylimidazole and the like are used. Among these, preferably imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1- Cyanoethyl-2-undecylimidazole is used.

(Phosphorus curing accelerator)
As the phosphorus curing accelerator, for example, triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine and the like are used.

<Additive compound>
In the phosphorus-containing curable resin composition of the present invention, for example, an additive compound such as a mold release agent, an inorganic filler, a coupling agent, a resin-modified product, or a colorant, as long as the object of the present invention is not impaired. Can be contained. These additive compounds may be used alone or in combination of two or more.

(Release agent)
The release agent is used, for example, for the purpose of improving the release from the mold during molding, and any conventionally known release agent can be used, and there is no particular limitation.
Specific examples of the release agent include ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and palmitic acid, and metal salts thereof, polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene, and the like. It is done. The above releasing agents may be used alone or in combination of two or more.

(Inorganic filler)
The inorganic filler is used, for example, for the purpose of suppressing the expansion / contraction due to the thermal cycle in addition to ensuring insulation, and any conventionally known one can be used without any particular limitation.
Specific examples of inorganic fillers include fused silica, crystalline silica, amorphous silica, alumina, calcium carbonate, calcium silicate, barium sulfate, talc, clay, magnesium oxide, aluminum oxide, beryllium oxide, iron oxide, oxidized Examples thereof include titanium, aluminum nitride, silicon nitride, boron nitride, mica, glass, quartz, and mica. In addition, these inorganic fillers may be used independently or may use 2 or more types together. Furthermore, you may mix and use the below-mentioned coupling agent. Among these inorganic fillers, for example, amorphous silica and crystalline silica are preferable in that the thermal expansion coefficient of the encapsulant can be reduced, thereby improving the connection reliability of the encapsulant. used.

(Coupling agent)
The coupling agent is used for the purpose of, for example, enhancing the adhesion between the inorganic filler and the resin component.
Specific examples of the coupling agent include various alkoxysilane compounds such as vinylalkoxysilane, epoxyalkoxysilane, styrylalkoxysilane, methacryloxyalkoxysilane, acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, and isocyanatealkoxysilane. Examples thereof include alkoxy titanium compounds and aluminum chelates. In addition, the said coupling agent may be used independently or may use 2 or more types together.

(Modified resin)
The resin-modified product is used for the purpose of finely adjusting various physical properties, and any conventionally known one can be used without any particular limitation.
Specific examples of the resin-modified product include a modified product of polybutadiene, a modified product of acrylonitrile copolymer, and the like. In addition, the said resin modified material may be used independently, or may use 2 or more types together.

(Coloring agent)
The colorant is used for the purpose of adjusting the appearance, and any conventionally known colorant can be used without any particular limitation.
Specific examples of the colorant include carbon black, phthalocyanine blue, and phthalocyanine green. In addition, the said coloring agent may be used independently, or may use 2 or more types together.

<Method for producing phosphorus-containing curable resin composition>
In the production of the phosphorus-containing curable resin composition of the present invention, the amount of the phosphorus-containing bisphenol compound, epoxy compound and phenol resin used should be specified relative to the hydroxyl value (KOHmg / g) in the phenol resin used. Can do.
That is, the use amount (mixing ratio) of the epoxy compound is such that the number of hydroxyl groups calculated from the hydroxyl value (KOHmg / g) of the phenol resin is 1, and the number of epoxy groups of the epoxy compound is preferably 0.5 to 4. The usage amount (mixing ratio) is such that the usage amount (mixing ratio) is preferably 0.5 to 2.5, and the usage amount is particularly preferably 0.5 to 1.5. Further, the amount (mixing ratio) of the phosphorus-containing bisphenol compound is such that the number of hydroxyl groups calculated from the hydroxyl value (KOHmg / g) of the phenol resin is 1, while the number of hydroxyl groups of the phosphorus-containing bisphenol compound is preferably 0.00. Amount used (mixing ratio) to be 001 to 1.0, more preferably a amount (mixing ratio) to be 0.001 to 0.5, particularly preferably 0.01 to 0.5. Use amount (mixing ratio).
Furthermore, the usage-amount of a hardening accelerator becomes like this. Preferably it is 0.1-10g with respect to 100g of mixtures containing a phosphorus containing bisphenol compound, an epoxy compound, and a phenol resin mix | blended in said range, More preferably, it is 0.2. -5 g, particularly preferably 0.4-2 g. The amount of the additive compound used is preferably 0 to 20 g, more preferably 0 to 10 g, particularly preferably 100 g of a mixture of the phosphorus-containing bisphenol compound, the epoxy compound, and the phenol resin blended in the above range. 0 to 6 g are used.

  The phosphorus-containing curable resin composition of the present invention includes, for example, a phenol resin having one or more phenolic hydroxyl groups in at least one molecule in the air or an inert gas environment, and an epoxy group in at least one molecule. Is produced by a method such as mixing an epoxy compound having two or more, at least one phosphorus-containing bisphenol compound, and at least one curing accelerator. As a specific example, there is a method of producing by performing an operation such as adding a phosphorus-containing bisphenol compound, an epoxy compound, and a curing accelerator in this order and mixing them while heating to around the softening point of the phenol resin to be used. Moreover, it can heat suitably and can also manufacture as a melt-molded product of a phosphorus containing curable resin composition. Further, it may be produced as a phosphorus-containing curable resin composition solution by separately adding an organic solvent to dissolve or slurry.

<Method for producing phosphorus-containing curable resin composition solution>
On the other hand, the phosphorus-containing curable resin composition is manufactured as a phosphorus-containing curable resin composition solution by adding an organic solvent separately from the start of manufacture to the end of manufacture in order to facilitate handling. May be.

<Organic solvent>
Such an organic solvent is not particularly limited as long as it is a solvent that volatilizes when the phosphorus-containing curable resin composition of the present invention is heat-cured. For example, aliphatic ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone) , Cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (diisopropyl ether, diphenyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,2-dimethoxyethane, etc.), halogenated hydrocarbons ( Dichloromethane, 1,2-dichloroethane, etc.), aromatic hydrocarbons (toluene, benzene, xylene, etc.), aprotic polar solvents (dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N- Methyl pyrrolidone, dimethyl Sulfoxide, etc.) and the like. In addition, the said organic solvent may be used independently, or may use 2 or more types together.

The amount of the organic solvent used is preferably 0.1 to 1000 mL, more preferably 0.5 to 500 mL, and particularly preferably 1 to 100 mL with respect to 1 g of the phosphorus-containing curable resin composition.
In addition, the phosphorus-containing curable resin composition solution is prepared by mixing the phosphorus-containing curable resin composition manufactured at the above-described mixing ratio and the organic solvent, and then mixing, stirring, ultrasonic treatment, and appropriate heat dissolution. Processing or the like may be performed.

  The present invention produces a phosphorous-containing curable resin composition or a phosphorous-containing curable resin composition solution with the above-described blending ratio, etc., for example, by sealing the electronic component in the electric and electronic industries. When used as a resin curing agent for a laminated board material, sufficient heat resistance and hydrolysis resistance are exhibited.

[Phosphorus-containing resin cured product]
Moreover, this invention provides the phosphorus containing curable resin composition which hardens the phosphorus containing curable resin composition mentioned above and the additional compound added as needed. Furthermore, it can also be set as the phosphorus containing resin hardened | cured material formed by making a phosphorus-containing curable resin composition and resin compounds other than a phenol resin react and harden | cure.

(Resin compound)
As the resin compound, a resin compound other than a phenol resin that can form a chemical bond by a curing reaction that reacts with the epoxy compound in the phosphorus-containing curable resin composition described above by the action of a curing accelerator is used. Can do.
Specific examples of such a resin compound preferably include melanin resin, polyamide resin, polyimide resin, polyurethane resin and the like. In addition, the said resin compound may be used individually or may use 2 or more types together.

In addition, the reaction between the resin compound and the phosphorus-containing curable resin composition is preferably performed in an amount of 0.01 to 1 g, and more preferably 0.001 to 1 g of the resin compound. 05 to 0.50 g, particularly preferably 0.1 to 0.30 g is used.
The present invention can exhibit sufficient heat resistance and hydrolysis resistance by reacting in the amounts used as described above, for example, for sealing electronic components in the electric and electronic industries. It is used as a cured resin for laminated board materials.

<Method for producing phosphorus-containing cured product>
(Curing conditions)
The phosphorus-containing resin cured product of the present invention cures, for example, a phosphorus-containing curable resin composition or a phosphorus-containing curable resin composition solution and a resin compound other than a phenol resin in the atmosphere or in an inert gas environment. Manufactured by. Furthermore, the manufacturing method of the hardened | cured material of this invention can be manufactured also by the method of heat-hardening, for example after shape | molding in a desired shape. Specific methods include, for example, a method of coating on various substrates such as a metal foil and a release film and heat-curing, a method of pouring into a mold and heat-curing, and the like. This is a method of coating on various substrates and forming into a film shape so as not to occur.

The curing temperature and curing reaction time in the curing reaction are not particularly limited because they can be appropriately adjusted, but are preferably performed at a curing temperature of 80 to 250 ° C.
Further, the step of heating and curing may be performed in one step, or may be performed in multiple steps, for example, by changing temperature conditions. Preferably, in order to remove volatile components generated during the curing reaction from the system. It is performed in a multi-step process in which curing is performed step by step at various curing temperatures. More specifically, heat curing is performed at the second curing temperature at a temperature of 140 ° C. to 200 ° C., which is a temperature higher than the curing temperature of the first step, and the first step of reacting at a temperature of 100 to 140 ° C. Perform in a multi-step process.

Furthermore, since the phosphorus-containing resin cured product of the present invention contains a phosphorus-containing bisphenol compound represented by the general formula (1) as a monomer component, it has flame retardancy and has a crosslinked structure, so that it is resistant to hydrolysis. Can be granted.
Accordingly, the cured phosphorus-containing resin of the present invention can prevent bleed-out of flame retardants and is excellent in flame retardancy and moisture absorption resistance. For example, electrical and electronic industries such as sealing materials such as LEDs This is useful for sealing electronic components in the field.

  Next, although it demonstrates concretely in an Example, this invention is not limited to these Examples, a reference example, etc.

[Reference Example 1]
<Phosphorus-containing compound represented by general formula (1): Formula (1-1)>

To a glass reaction vessel equipped with a thermometer, temperature control device, dropping device and stirring means, 75 mL of toluene and 10.1 g (0.05 mol) of diphenylphosphine oxide were added, and then 6.1 g of 4-hydroxybenzaldehyde was added thereto. (0.05 mol) and 5.17 g (0.055 mol) of phenol were sequentially added, and the mixture was stirred at 65 ° C. for 1 hour. Thereafter, 0.2 g (0.001 mol) of p-toluenesulfonic acid was added thereto, and the mixture was further heated to 110 ° C. and stirred for 8 hours to carry out a reaction. After completion of the reaction, the resulting reaction mixture was cooled to room temperature and filtered to obtain a residue, and the residue was further washed with 30 mL of toluene to obtain a solid. Next, the obtained solid was suspended in 100 mL of acetonitrile, stirred at 80 ° C. for 1 hour, and then cooled to room temperature. The solid matter was filtered off from the resulting suspension, and this solid matter was further washed with cold acetonitrile and dried. As a white powder, the desired product, bis (4-hydroxyphenyl) methyldiphenylphosphine oxide, 16. 9 g was obtained (acquisition yield: 84.3%).
Analytical values of the obtained bis (4-hydroxyphenyl) methyldiphenylphosphine oxide were as follows.

MS spectrum [CI-MS]: 401 [M + 1]
¹ H-NMR spectrum [300 MHz, d6-DMSO, δ (ppm)]: 5.28 (1H, d), 6.53 (4H, d), 7.32-7.43 (10H, brs), 7 .75-7.82 (4H, brs), 9.16 (2H, s)
Melting point: 301 ° C

[Reference Example 2]
<Phosphorus-containing compound represented by general formula (1): Formula (1-2)>

To a glass reaction vessel equipped with a thermometer, a temperature adjusting device, a dropping device and a stirring measure, 2.02 g (0.01 mol) of diphenylphosphine oxide was added, and then 1.22 g (0.2 .0 g) of 2-hydroxybenzaldehyde was added thereto. 01 mol) and 5.70 g (0.05 mol) of phenol were sequentially added, and the mixture was stirred at 65 ° C. for 1.5 hours. Next, 0.02 g (0.0001 mol) of p-toluenesulfonic acid was added thereto, and the mixture was further heated to 110 ° C. and stirred for 3 hours to carry out a reaction. After completion of the reaction, when the obtained reaction solution was dropped into 20 mL of toluene, a precipitate was formed. The produced precipitate was filtered off and further washed with 20 mL of toluene. The obtained precipitate was dried to obtain 3.21 g of ((2-hydroxyphenyl) (4-hydroxyphenyl) methyl) diphenylphosphine oxide represented by the formula (1-2) as a target product as a white powder ( Acquisition yield: 80.3%).
Analytical values of the obtained ((2-hydroxyphenyl) (4-hydroxyphenyl) methyl) diphenylphosphine oxide were as follows.

MS spectrum [CI-MS]: 401 [M + 1]
¹ H-NMR spectrum [300 MHz, d ₆ -DMSO, δ (ppm)]: 5.49 (1H, d), 6.52 (2H, d), 6.65-6.69 (2H, brs), 6.89-6.94 (2H, brs), 7.22-7.26 (2H, brs), 7.34-7.46 (6H, brs), 7.64-7.79 (4H, brs) ), 7.91-7.94 (1H, brs), 9.20 (1H, s), 9.77 (1H, s)

[Reference Example 3]
<Phosphorus-containing compound represented by general formula (1): Formula (1-3)>

To a glass reaction vessel equipped with a thermometer, temperature control device, dropping device and stirring means, 75 mL of toluene and 10.1 g (0.05 mol) of diphenylphosphine oxide were added, and then 6.1 g of 4-hydroxybenzaldehyde was added thereto. (0.05 mol) and 5.95 g (0.055 mol) of cresol were sequentially added, and the mixture was stirred at 65 ° C. for 1 hour. Next, 0.2 g (0.001 mol) of p-toluenesulfonic acid was added thereto, and the mixture was further heated to 110 ° C. and stirred for 8 hours to carry out a reaction. After completion of the reaction, the resulting reaction suspension was cooled to room temperature, the precipitate was filtered off, and further washed with 30 mL of toluene. The obtained solid was suspended in 100 mL of acetonitrile and stirred at 80 ° C. for 1 hour, then cooled to 0 ° C., the precipitate was filtered off, and washed with cold acetonitrile. The obtained solid was dried to obtain 17.8 g of (4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyldiphenylphosphine oxide represented by the formula (1-3) as the target product as a white powder. (Acquisition yield: 89.5%).
Analytical values of the obtained (4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyldiphenylphosphine oxide were as follows.

MS spectrum [CI-MS]: 415 [M + 1]
¹ H-NMR spectrum [300 MHz, d6-DMSO, δ (ppm)]: 1.96 (3H, d), 5.24 (1H, d), 6.51-6.54 (3H, brs), 7 18-7.20 (2H, brs), 7.31-7.38 (8H, brs), 7.74-7.83 (4H, brs), 9.09 (2H, s)
Melting point: 252 ° C

[Example 1]
<Production of phosphorus-containing curable resin composition solution>
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure, 0.2007 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [formula (1-1)] and a phenol novolac resin (HF manufactured by Meiwa Kasei) -1M: Softening point 84 ° C., hydroxyl group equivalent 106 g / eq) 1.9989 g of dimethylacetamide was added to a mixture of 1.8052 g and 0.0172 g of 2-undecylimidazole to obtain a uniform solution at 100 ° C. Next, 2.1846 g of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (manufactured by Daicel Chemical Industries, Celoxide 2021P) is added to this solution, and a phosphorus-containing curable resin is formed as a uniform solution. A composition solution was obtained.
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-1A) was obtained (the following reaction formula [5-1A]).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 1, in Example 1, the residual weight ratio of carbide at 1000 ° C. was 8.8%.

[Example 2]
<Production of phosphorus-containing curable resin composition solution>
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure, 0.4012 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [formula (1-1)] and phenol novolak resin (HF manufactured by Meiwa Kasei) -1M: Softening point 84 ° C., hydroxyl value 106 g / eq) To a mixture of 1.6092 g and 0.0175 g of 2-undecylimidazole, 4.0225 g of dimethylacetamide was added to obtain a uniform solution at 100 ° C. Next, 2.0219 g of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (manufactured by Daicel Chemical Industries, Celoxide 2021P) is added to this solution, and a phosphorus-containing curable resin composition is formed as a uniform solution. A product solution was obtained.
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-1B) was obtained (the following reaction formula [5-1B]).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 2, in Example 2, the remaining weight ratio of carbide at 1000 ° C. was 8.5%.

[Comparative Example 1]
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure, phenol novolak resin (HF-1M manufactured by Meiwa Kasei Co., Ltd .: softening point 84 ° C., hydroxyl value 106 g / eq) 1.0016 g and 2-undecylimidazole To a mixture of 0.0162 g, 1.0021 g of dimethylacetamide was added to obtain a uniform solution at room temperature. To this solution, 1.1809 g of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Daicel Chemical Industries, Celoxide 2021P) was added to obtain a uniform solution. After filling the container, the cured epoxy resin (Ref. 1) was obtained by heating in an oven at 160 to 170 ° C. for 5 hours (the following reaction formula [Ref. 1]). The obtained cured epoxy resin (Ref. 1) did not contain dimethylacetamide.

About 10 mg of the resulting cured epoxy resin was weighed accurately and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 3, in Comparative Example 1 not containing bis (4-hydroxyphenyl) methyldiphenylphosphine oxide, the remaining weight ratio of carbide at 1000 ° C. is 4.2%, and bis (4-hydroxyphenyl) Phosphorus of Example 1 (FIG. 1, residual weight ratio 8.8%) and Example 2 (FIG. 2, residual weight ratio 8.5%) containing methyldiphenylphosphine oxide [formula (1-1)] It was found that the cured resin containing resin has a higher residual weight ratio after the heat resistance experiment and is less flammable even at a high temperature, that is, excellent in flame retardancy.

[Example 3]
<Production of phosphorus-containing curable resin composition solution>
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure, 0.2012 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [formula (1-1)] and a phenol novolak resin (HF manufactured by Meiwa Kasei) −1M: Softening point 84 ° C., hydroxyl group equivalent 106 g / eq) To a mixture of 0.8056 g and 2-undecylimidazole 0.0110 g, 2.0061 g of dimethylacetamide was added to obtain a uniform solution at 110 ° C. Next, 1.5386 g of 2,2-bis (4-glycidyloxyphenyl) propane (manufactured by Mitsubishi Chemical Corporation, jER828: epoxy equivalent 184-194 g / eq) was added to this solution, and a phosphorus-containing curable resin composition was formed as a uniform solution. A solution was obtained.
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-1C) was obtained (the following reaction formula [5-1C]).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 4, in Example 3, the residual weight ratio of carbides at 1000 ° C. was 22.2%.

[Example 4]
<Production of phosphorus-containing curable resin composition solution>
In a glass reaction vessel equipped with a thermometer, a temperature adjusting device, and a stirring measure, 0.2023 g of ((2-hydroxyphenyl) (4-hydroxyphenyl) methyl) diphenylphosphine oxide [formula (1-2)], Phenol novolac resin (BRG-556, Showa Denko, softening point 77-83 ° C., hydroxyl group equivalent 103-106 g / eq) 0.8066 g, 2,2-bis (4-glycidyloxyphenyl) propane (Mitsubishi Chemical, jER828) : Epoxy equivalent 184-194 g / eq) 1.5386 g and 2-undecylimidazole 0.0254 g to a mixture of dimethylacetamide 1.50221 g to obtain a phosphorus-containing curable resin composition solution as a uniform solution at room temperature .
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-2A) was obtained (the following reaction formula [5-2A]).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 5, in Example 4, the remaining weight ratio of carbide at 1000 ° C. was 21.0%.

[Example 5]
<Production of phosphorus-containing curable resin composition solution>
A ((4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyl) diphenylphosphine oxide [formula (1-3)] 0 was added to a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure. 2007 g, phenol novolak resin (manufactured by Showa Denko, BRG-556: softening point 77-83 ° C., hydroxyl group equivalent 103-106 g / eq) 0.8025 g, 2,2-bis (4-glycidyloxyphenyl) propane ( (Mitsubishi Chemical, jER828: Epoxy equivalent 184-194 g / eq) 1.5168 g and 2-ethyl-methylimidazole 0.0258 g to a mixture of dimethylacetamide 2.5055 g, a phosphorus-containing curable resin as a uniform solution at room temperature A composition solution was obtained.
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-3A) was obtained (the following reaction formula [5-3A]).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 6, in Example 5, the residual weight ratio of carbide at 1000 ° C. was 24.9%.

[Comparative Example 2]
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure, 1.4965 g of phenol novolac resin (Maywa Kasei HF-1M: softening point 84 ° C., hydroxyl group equivalent 106 g / eq) and 2-undecylimidazole To a mixture of 0.0147 g, 1.5021 g of dimethylacetamide was added to obtain a uniform solution at room temperature. 1.0010 g of this solution was taken and 0.8921 g of 2,2-bis (4-glycidyloxyphenyl) propane (Mitsubishi Chemical, jER828: epoxy equivalent 184-194 g / eq) was added to make a uniform solution. After filling a 4 cm circular container, the cured epoxy resin (Ref. 2) was obtained by heating at 160 to 170 ° C. for 6 hours in an oven (the following reaction formula [Ref. 2]). The obtained cured epoxy resin (Ref. 2) did not contain dimethylacetamide.

About 10 mg of the obtained cured epoxy resin was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 7, in the cured product of Comparative Example 2 that does not contain bis (4-hydroxyphenyl) methyldiphenylphosphine oxide, the remaining weight ratio of carbide at 1000 ° C. is 14.7%, and bis (4-hydroxyphenyl) methyl is obtained. Example 3 containing diphenylphosphine oxide [formula (1-1)] (FIG. 4, residual weight ratio 22.2%), ((2-hydroxyphenyl) (4-hydroxyphenyl) methyl) diphenylphosphine oxide Example 4 (FIG. 5, residual weight ratio 21.0%) containing (Formula (1-2)] and ((4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyl) diphenyl The cured phosphorus-containing resin of Example 5 (FIG. 6, residual weight ratio 24.9%) containing phosphine oxide [formula (1-3)] A high residual weight ratio after the heat resistance experiments, hardly burned at high temperatures, i.e., it was found to be excellent in flame retardancy.

[Example 6]
<Production of phosphorus-containing curable resin composition solution>
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure, 0.4017 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [formula (1-1)] and phenol novolac resin (MEH Kasei MEH) -7851: Softening point 83 ° C., hydroxyl equivalent 218 g / eq) To a mixture of 1.6125 g and 2-undecylimidazole 0.0200 g, 4.0121 g of dimethylacetamide was added to obtain a uniform solution at 100 ° C. Next, 1.1770 g of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (manufactured by Daicel Chemical Industries, Celoxide 2021P) was added to this solution to obtain a phosphorus-containing curable resin as a uniform solution. A composition solution was obtained.
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-1D) was obtained (the following reaction formula [5-1D).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 8, in Example 6, the residual weight ratio of carbide at 1000 ° C. was 16.8%.

[Example 7]
<Production of phosphorus-containing curable resin composition solution>
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure, 0.4008 g of ((2-hydroxyphenyl) (4-hydroxyphenyl) methyl) diphenylphosphine oxide [formula (1-2)], 1.6196 g of phenol novolak resin (Maywa Kasei, MEH-7785: softening point 83 ° C., hydroxyl equivalent 218 g / eq), 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (Daicel Chemical) Industrial, Celoxide 2021P) 1.1808 g and 2-undecylimidazole 0.0336 g were mixed with dimethylacetamide 3.2162 g to obtain a phosphorus-containing curable resin composition solution as a uniform solution.
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-2B) was obtained (the following reaction formula [5-2B]).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 9, in Example 7, the residual weight ratio of carbide at 1000 ° C. was 16.1%.

[Example 8]
<Production of phosphorus-containing curable resin composition solution>
A ((4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyl) diphenylphosphine oxide [formula (1-3)] 0 was added to a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure. 2055 g, phenol novolac resin (Maywa Kasei, MEH-7851; softening point 83 ° C .; acid group equivalent 218 g / eq) 0.8033 g, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene 1.58746 g of dimethylacetamide was added to a mixture of 0.5922 g of carboxylate (Daicel Chemical Industries, Celoxide 2021P) and 0.0166 g of 2-undecylimidazole to obtain a phosphorus-containing curable resin composition solution as a uniform solution. .
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-3B) was obtained (the following reaction formula [5-3B]).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 10, in Example 8, the residual weight ratio of carbide at 1000 ° C. was 19.0%.

[Comparative Example 3]
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirrer, phenol novolac resin (Maywa Kasei, MEH-7851: softening point 83 ° C., hydroxyl equivalent 218 g / eq) 1.0012 g and 2-undecyl To a mixture of 0.0102 g of imidazole, 1.0061 g of dimethylacetamide was added at room temperature to obtain a uniform solution. To this solution, 0.5811 g of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Daicel Chemical Industries, Celoxide 2021P) was added to make a uniform solution, and this solution was formed into a circular shape having a diameter of 4 cm. After filling the container, the cured epoxy resin (Ref. 3) was obtained by heating in an oven at 160 to 170 ° C. for 6 hours (the following reaction formula [Ref. 3]). The obtained cured epoxy resin (Ref. 3) did not contain dimethylacetamide.

About 10 mg of the obtained epoxy resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 11, in the cured product of Comparative Example 3 that does not contain bis (4-hydroxyphenyl) methyldiphenylphosphine oxide, the remaining weight ratio of carbide at 1000 ° C. is 11.5%, and bis (4-hydroxyphenyl) methyl Example 6 containing diphenylphosphine oxide [formula (1-1)] (FIG. 8, residual weight ratio 16.8%), ((2-hydroxyphenyl) (4-hydroxyphenyl) methyl) diphenylphosphine oxide Example 7 containing [Formula (1-2)] (FIG. 9, residual weight ratio 16.1%) and ((4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyl) diphenyl Phosphorus-containing resin cured product of Example 8 (FIG. 10, residual weight ratio 19.0%) containing phosphine oxide [formula (1-3)] It is a high residual weight ratio after the heat resistance experiments, hardly burned at high temperatures, i.e., it was found to be excellent in flame retardancy.

[Example 9]
<Production of phosphorus-containing curable resin composition solution>
In a glass reaction vessel equipped with a thermometer, a temperature adjusting device, and a stirring measure, 0.2024 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [formula (1-1)] and a phenol novolac resin (Maywa Kasei, MEH-7851 (softening point 83 ° C., hydroxyl group equivalent 218 g / eq) To a mixture of 0.8034 g and 2-undecylimidazole 0.0101 g, dimethylacetamide 2.0059 g was added to obtain a uniform solution at 110 ° C. Next, 0.8905 g of 2,2-bis (4-glycidyloxyphenyl) propane (Mitsubishi Chemical Co., Ltd., jER828; epoxy equivalent 184-194 g / eq) was added to this solution, and a phosphorus-containing curable resin composition was formed as a uniform solution. A solution was obtained.
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-1E) was obtained (the following reaction formula [5-1E]).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 12, in Example 9, the residual weight ratio of carbide at 1000 ° C. was 25.7%.

[Comparative Example 4]
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirrer, 1.1021 g of phenol novolac resin (Maywa Kasei, MEH-7851, softening point 83 ° C., hydroxyl equivalent 218 g / eq) and 2-undecyl To a mixture of 0.0129 g of imidazole, 1.0987 g of dimethylacetamide was added to obtain a uniform solution at room temperature. 0.4342 g of 2,2-bis (4-glycidyloxyphenyl) propane (Mitsubishi Chemical Co., Ltd., jER828; epoxy equivalent 184-194 g / eq) was added to 1.0072 g of this solution to make a uniform solution, and this solution was circular with a diameter of 4 cm. Then, the cured epoxy resin (Ref. 4) was obtained by heating in an oven at 160 to 170 ° C. for 6 hours (the following reaction formula [Ref. 4]). The obtained cured epoxy resin (Ref. 4) did not contain dimethylacetamide.

About 10 mg of the obtained cured epoxy resin was weighed accurately, and thermogravimetric analysis (TGA) measurement was performed with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 13, in the cured product of Comparative Example 4 that does not contain bis (4-hydroxyphenyl) methyldiphenylphosphine oxide, the residual weight ratio of carbide at 1000 ° C. is 16.8%, and bis (4-hydroxyphenyl) methyl The phosphorus-containing resin cured product of Example 9 (FIG. 12, residual weight ratio 25.7%) containing diphenylphosphine oxide [Formula (1-1)] has a higher residual weight ratio after the heat resistance experiment. It was found that it is difficult to burn even at high temperatures, that is, excellent in flame retardancy.

[Example 10]
<Production of phosphorus-containing curable resin composition solution>
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure, 0.2010 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [formula (1-1)] and a phenol novolak resin (manufactured by Showa Denko) , BRG-556: softening point 77-83 ° C .; hydroxyl equivalent 103-106 g / eq) 0.8069 g, and cresol novolac resin (manufactured by DIC, Epicron N-673: softening point 73-82 ° C .; epoxy equivalent 205) -215 g / eq) 1.6522 g and 0.0270 g of triphenylphosphine were added with 2.6931 g of dimethylacetamide to obtain a phosphorus-containing curable resin composition solution as a uniform solution at 100 ° C.
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-1E) was obtained (the following reaction formula [5-1E]).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 14, in Example 10, the residual weight ratio of carbide at 1000 ° C. was 34.7%.

[Comparative Example 5]
In a glass reaction vessel equipped with a thermometer, a temperature adjusting device, and a stirring measure, a cresol novolac resin (manufactured by DIC, Epicron N-673: softening point 73-82 ° C .; epoxy equivalent 205-215 g / eq) 2 .0027 g, a mixture of phenol novolac resin (manufactured by Showa Denko, BRG-556: softening point 77-83 ° C .; hydroxyl group equivalent 103-106 g / eq) 1.0158 g and triphenylphosphine 0.0318 g, dimethylacetamide 2.2900 g Was added to obtain a uniform solution at room temperature. This solution was filled in a circular container having a diameter of 4 cm and then heated in an oven at 160 to 170 ° C. for 5 hours to obtain a solid. When the obtained solid was analyzed, it was confirmed that dimethylacetamide was contained. Therefore, this solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and the target epoxy resin was obtained. A cured product (Ref. 5) was obtained (the following reaction formula [Ref. 5]).

About 10 mg of the obtained cured epoxy resin was weighed accurately and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 15, in Comparative Example 5 that does not contain bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [Formula (1-1)], the residual weight ratio of carbide at 1000 ° C. is 29.2%. The cured phosphorus-containing resin of Example 10 (FIG. 14, residual weight ratio 34.7%) containing bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [formula (1-1)] It was found that the residual weight ratio after the heat resistance experiment was high and it was difficult to burn even at high temperatures, that is, excellent in flame retardancy.

[Example 11]
<Production of phosphorus-containing curable resin composition solution>
A ((4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyl) diphenylphosphine oxide [formula (1-3)] 0 was added to a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure. 2007 g, phenol novolak resin (manufactured by Showa Denko, BRG-556: softening point 77-83 ° C .; hydroxyl group equivalent 103-106 g / eq) 0.8046 g, and cresol novolac resin (manufactured by DIC, Epicron N-673) : Softening point 73-82 ° C .; epoxy equivalent 205-215 g / eq) 1.6772 g and 0.0288 g of 2-undecylimidazole 2.65.6 g of dimethylacetamide was added and cured with phosphorus as a uniform solution at 100 ° C. A functional resin composition solution was obtained.
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-3C) was obtained (the following reaction formula [5-3C]).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 16, in Example 11, the residual weight ratio of carbide at 1000 ° C. was 37.5%.

[Comparative Example 6]
In a glass reaction vessel equipped with a thermometer, a temperature adjusting device, and a stirring measure, a cresol novolac resin (manufactured by DIC, Epicron N-673: softening point 73-82 ° C .; epoxy equivalent 205-215 g / eq) 2 Dimethylacetamide 3.0.0172 g, phenol novolac resin (BRG-556, Showa Denko BRG-556: softening point 77-83 ° C., hydroxyl equivalent 103-106 g / eq) 1.0026 g and 2-undecylimidazole 0.0309 g. 0281 g was added to make a uniform solution at room temperature. This solution was filled in a circular container having a diameter of 4 cm and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. When the obtained solid was analyzed, it was confirmed that dimethylacetamide was contained. Therefore, this solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and the target epoxy resin was obtained. A cured product (Ref. 6) was obtained (the following reaction formula [Ref. 6]).

About 10 mg of the obtained cured epoxy resin was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 17, in Comparative Example 6 not containing ((4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyl) diphenylphosphine oxide [formula (1-3)], the remaining carbide at 1000 ° C. Example 11 having a weight ratio of 28.2% and containing ((4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) methyl) diphenylphosphine oxide [formula (1-3)] It was found that the phosphorus-containing cured resin (FIG. 16, residual weight ratio 37.5%) has a higher residual weight ratio after the heat resistance experiment and is not easily combusted at high temperatures, that is, excellent in flame retardancy. .
Moreover, even if the curing accelerator is changed from triphenylphosphine to 2-undecylimidazole by comparison with the residual weight ratio of 29.2% in Comparative Example 5, the residual weight ratio of carbide at 1000 ° C. is the same. It can be seen that

[Example 12]
<Production of phosphorus-containing curable resin composition solution>
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure, 0.2030 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [Formula (1-1)] and a phenol novolac resin (Maywa Kasei) MEH-7851: Softening point 83 ° C .; hydroxyl group equivalent 218 g / eq) 0.8001 g and cresol novolac resin (DIC, Piclone N-673: softening point 73-82 ° C .; epoxy equivalent 205-215 g / eq) as epoxy resin ) 2.9968 g of dimethylacetamide was added to a mixture of 0.9838 g and 0.0200 g of 2-undecylimidazole to obtain a phosphorus-containing curable resin composition solution as a uniform solution at 110 ° C.
<Manufacture of cured resin containing phosphorus>
The obtained phosphorus-containing curable resin composition solution was filled in a circular container having a diameter of 4 cm, and then heated in an oven at 160 to 170 ° C. for 6 hours to obtain a solid. Analysis of the resulting solid confirmed that it contained dimethylacetamide. The solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and contained the target phosphorus-containing product. A cured resin (5-1F) was obtained (the following reaction formula [5-1F]).

About 10 mg of the obtained phosphorus-containing resin cured product was accurately weighed and subjected to thermogravimetric analysis (TGA) measurement using TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 18, in Example 12, the residual weight ratio of carbide at 1000 ° C. was 38.0%.

[Comparative Example 7]
In a glass reaction vessel equipped with a thermometer, a temperature control device, and a stirring measure, a cresol novolak resin (manufactured by DIC, Epicron N-673: softening point 73-82 ° C .; epoxy equivalent 205-215 g / eq) 1 .0086 g, 2.0103 g of dimethylacetamide was added to a mixture of 1.0381 g of phenol novolac resin (Maywa Kasei, MEH-7851; softening point 83 ° C .; hydroxyl group equivalent 218 g / eq) and 0.0218 g of 2-undecylimidazole. Then, the solution was made uniform at room temperature, and this solution was filled in a circular container having a diameter of 4 cm. When the obtained solid was analyzed, it was confirmed that dimethylacetamide was contained. Therefore, this solid was dried at 250 ° C. for 1 hour to distill off dimethylacetamide, and the target epoxy resin was obtained. A cured product (Ref. 7) was obtained (the following reaction formula [Ref. 7]).

About 10 mg of the resulting cured epoxy resin was weighed and accurately weighed, and thermogravimetric analysis (TGA) measurement was performed with TG / DTA320 (manufactured by Seiko Denshi Kogyo). The results are shown in FIG.
From FIG. 19, in the cured product of Comparative Example 7 not containing bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [formula (1-1)], the residual weight ratio of carbide at 1000 ° C. was 28.7%, The cured phosphorus-containing resin of Example 12 (FIG. 18, residual weight ratio 38.0%) containing bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [formula (1-1)] is more heat resistant. It was found that the residual weight ratio after the experiment was high and it was difficult to burn even at high temperatures, that is, excellent in flame retardancy.

[Reference Example 4]
In a 300 mL glass reaction vessel, 50.0 g of phenol resin (BRG-556 manufactured by Showa Denko: phenolic hydroxyl value 105 g / eq) was weighed and melted at 150 ° C., and then epoxy resin (Mitsubishi Chemical, jER828; (Epoxy value 184-194 g / eq) 90.5 g was added and stirred well. Further, 0.90 g of 1-cyanoethyl-2-undecylimidazole (Cureazole C11Z-CN manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added as a curing accelerator at 120 ° C., and stirring was continued to obtain a viscous solution. This viscous solution was poured into a mold, and finally cured at 180 ° C. for 5 hours to obtain a resin plate.

[Comparative Example 8]
<Manufacture of phosphorus compound mixed type resin plate: phosphorus atom content in total amount of phosphorus-containing compound, epoxy compound, and phenol resin: 2.01% by mass>
In a 300 mL glass reaction vessel, 27.7 g of phenol resin (BRG-556 manufactured by Showa Denko: phenolic hydroxyl value 105 g / eq) was weighed and melted at 150 ° C., and then epoxy resin (JER828 manufactured by Mitsubishi Chemical): epoxy was used. (Valence: 184 to 194 g / eq) 50.1 g, and 22.2 g of resorcinol bisdi (2,6-dimethylphenol) phosphate (Daihachi Chemical PX-200) as a phosphorus-containing compound were added and stirred well. Furthermore, 0.50 g of 1-cyanoethyl-2-undecylimidazole (Curesol C11Z-CN manufactured by Shikoku Kasei Kogyo) was added as a curing accelerator at 120 ° C., and stirring was continued to obtain a viscous solution. This viscous solution was poured into a mold, and finally cured at 190 ° C. for 10 hours to obtain a phosphorus compound mixed resin plate.
In addition, the content rate of the phosphorus atom of the comparative example 8 is the amount (g) of the phosphorus-containing compound with respect to the total usage amount (g) of the phosphorus-containing compound, the epoxy compound, and the phenol resin used, and the phosphorus-containing compound used ( The total phosphorus atomic weight (molecular weight: 31 × number) in the molecular weight was calculated as mass%.

[Comparative Example 9]
<Manufacture of phosphorus compound mixed resin plate: phosphorus atom content in total amount of phosphorus-containing compound, epoxy compound, and phenol resin: 0.90% by mass>
In a 300 mL glass reaction vessel, 12.5 g of 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide as an phosphorus-containing compound and an epoxy resin (Mitsubishi Chemical jER828: (Epoxy value: 184 to 194 g / eq) 82.5 g was weighed and 0.82 g of triphenylphosphine was added, and the mixture was well dispersed by stirring at room temperature for about 30 minutes. The container was then immersed in a 140 ° C. oil bath and allowed to react until the contents were clear. After becoming transparent, stirring was continued for 2 hours.
In another 300 mL glass reaction vessel, 37.5 g of phenol resin (BRG-556 manufactured by Showa Denko: phenolic hydroxyl value 105 g / eq) was taken and heated to 150 ° C. The previous reaction transparency was added in four portions. The transparent reaction solution was brought to 120 ° C., and 0.82 g of 1-cyanoethyl-2-undecylimidazole (Cureazole C11Z-CN, manufactured by Shikoku Kasei Kogyo) was added as a curing accelerator, and stirring was continued to obtain a viscous solution. This viscous solution was poured into a mold, and finally cured at 190 ° C. for 10 hours to obtain a resin plate.
The phosphorus atom content in Comparative Example 9 was calculated by the same method as in Comparative Example 8.

[Example 13]
<Manufacture of a phosphorus compound mixed type resin plate: phosphorus atom content in the total amount of phosphorus-containing bisphenol compound, epoxy compound, and phenol resin: 0.59% by mass>
In a 300 mL glass reaction vessel, 10.0 g of bis (4-hydroxyphenyl) methyldiphenylphosphine oxide [Formula (1-1)] and an epoxy resin (Mitsubishi Chemical jER828: epoxy value 184 to 194 g / eq) 81.9 g After adding 0.82 g of triphenylphosphine, the mixture was stirred at room temperature for about 30 minutes and well dispersed. The container was then immersed in a 140 ° C. oil bath and allowed to react until the contents were clear. After becoming transparent, stirring was continued for 2 hours.
In another 300 mL glass reaction vessel, 40.0 g of phenol resin (BRG-556 manufactured by Showa Denko: phenolic hydroxyl value 105 g / eq) was taken and heated to 150 ° C. The previous reaction transparency was added in four portions. The transparent reaction solution was brought to 120 ° C., and 0.82 g of 1-cyanoethyl-2-undecylimidazole (Cureazole C11Z-CN, manufactured by Shikoku Kasei Kogyo) was added as a curing accelerator, and stirring was continued to obtain a viscous solution. This viscous solution was poured into a mold, and finally cured at 190 ° C. for 10 hours to obtain a resin plate.
In addition, the content rate of the phosphorus atom of Example 13 is the amount (g) of the phosphorus-containing bisphenol compound used relative to the total amount (g) of the phosphorus-containing bisphenol compound, the epoxy compound, and the phenol resin used, and the phosphorus content used. From the total phosphorus atomic weight (the atomic weight of phosphorus: 31 × number) in the bisphenol compound (molecular weight), it was calculated in mass%.

[Evaluation]
(Flame retardance)
From the resin plates obtained in Reference Example 4, Comparative Example 8, Comparative Example 9, and Example 13, a test piece (length 125 mm, width 13 mm, according to the UL94V standard, which is a general flame retardancy determination method, Five pieces each having a thickness of 3 mm) were produced and subjected to a vertical combustion test. Next, in accordance with the standards described in UL94V (test method), grades such as V-0, V-1, or V-2 are evaluated, while the flame retardancy that does not reach the UL94V standard is low ( (Or nothing) was considered non-conforming. The results are shown in Table 1 below.

  From Table 1, it turns out that there exists the outstanding flame-retardant effect (Example 13: V-0) by containing the specific phosphorus containing bisphenol compound of this invention. Further, from Example 13 (0.59% by mass), the phosphorus atom content in the phosphorus compound-mixed resin plate of the present invention is Comparative Example 8 (2.01% by mass) and Comparative Example 9 (0.90). Despite being less than the phosphorus atom content in mass%), from Table 1, the phosphorus compound-mixed resin plate of the present invention (Example 13) is more than the resin plates of Comparative Example 8 and Comparative Example 9. It can be seen that the flame retardancy is excellent.

  The present invention relates to a phosphorus-containing curable resin composition containing a bifunctional phosphorus-containing compound and a phosphorus-containing resin cured product in which a phosphorus atom obtained by curing it is incorporated into a resin skeleton. The curable resin composition is useful, for example, as a sealing material for electronic parts, a laminate material, etc. in the electric and electronic industries because the cured product exhibits excellent flame retardancy.

Claims (4)

At least one phosphorus-containing bisphenol compound represented by the following general formula (1), at least one epoxy compound having two or more epoxy groups in one molecule, at least one molecule having one or more phenolic hydroxyl groups A phosphorus-containing curable resin composition comprising a phenol resin and at least one curing accelerator.

[In General Formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a fluorine atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. An oxy group, an aryl group having 6 to 18 carbon atoms which may have a substituent, or an aryloxy group having 6 to 18 carbon atoms which may have a substituent is shown. p, q, r, and s are each independently an integer of 0 to 4. R ⁵ is a hydrogen atom, a fluorine atom, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have an alkyloxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, or a carbon number. The C6-C12 aryl group which may have a C1-C6 alkyl group and a C1-C6 alkyloxy group is shown. ]   The phosphorus-containing curable resin according to claim 1, wherein the epoxy compound having two or more epoxy groups in the molecule is at least one epoxy compound selected from the group consisting of a diepoxide compound, a triepoxide compound, and a polyepoxide compound. Composition.   A phenol resin having at least one phenolic hydroxyl group is a polycondensation product of phenols, bisphenols, naphthols and aldehydes, polycondensation products of phenols and dienes, and polycondensation of phenols and ketones. The phosphorus containing curable resin composition of Claim 1 or 2 which is at least 1 sort (s) of phenol resin chosen from the group which consists of a thing.   A cured phosphorus-containing resin obtained by curing the phosphorus-containing curable resin composition according to any one of claims 1 to 3.

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