JP2017001984A - Phosphorus compound and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphorus compound as a curing accelerator capable of making flowability and curability of an epoxy resin composition excellent and suppressing Clconcentration in a cured article and a manufacturing method therefor.SOLUTION: There is provided a phosphorus compound represented by the formula (1). There is provided a method for manufacturing the phosphorus compound by an addition reaction of a corresponding phosphine compound and an epoxy compound. (1), where R is an alkyl group, an aryl group, a bi- or higher valent organic group, modified/unmodified phenol novolak type resin main chain skeleton or the like, X1 to X3 are each independently H, a C1 to 8 alkyl group or the like, l is an integer of 1 or more and m is an integer of 0 or more.SELECTED DRAWING: None

Description

  The present invention relates to a phosphorus compound and a method for producing the same.

  2. Description of the Related Art Conventionally, electrical and electronic parts such as semiconductor elements have been widely sealed with a thermosetting resin, and an epoxy resin is generally used as a sealing resin. In particular, epoxy resin compositions in which a phenol resin is used as a curing agent and an inorganic filler such as silica powder is blended are widely used because they are excellent in moldability and reliability and are inexpensive. In such an epoxy resin composition for sealing, the curing reaction between the epoxy resin and the curing agent needs to be completed within a predetermined time. When the curing of the epoxy resin composition is not completed within a predetermined time, the curing of the epoxy resin composition continues after the semiconductor element is sealed. For this reason, peeling of a semiconductor element and hardened | cured material occurs by volume change of hardened | cured material, and will cause a fatal defect as a semiconductor element apparatus. Therefore, for the purpose of completing the curing within a predetermined time, a curing accelerator is blended in the epoxy resin composition.

  As the curing accelerator, amine compounds such as tertiary amines and imidazoles, and phosphorus compounds such as phosphines and quaternary phosphonium salts are generally used. Further, addition reaction product of specific triphenylphosphine and quinone compound (for example, Patent Document 1), addition compound of tertiary phosphine and benzoquinone (for example, Patent Document 2), molecular compound of phosphonium and phenolic compound Etc. (for example, patent document 3) are also used.

Japanese Patent No. 4172605 Japanese Patent No. 4565503 JP 2004-231765 A

  Further, in order to ensure electrical continuity between the semiconductor element and the circuit, the semiconductor element is provided with a wire. In order to manufacture a semiconductor device obtained by molding a semiconductor element having a wire stretched with an epoxy resin composition at low cost, the wire material is being changed from gold to silver and further to copper. In addition, an epoxy resin, which is one of the raw materials in the epoxy resin composition, is usually obtained by reacting a phenol compound with epichlorohydrin. Therefore, impurity chlorine such as hydrolyzable chlorine is contained in the epoxy resin. include. Therefore, there is a problem that the copper wire is corroded by generated chlorine ions when the epoxy resin composition is heated and melted and pressure-molded.

In order to prevent the failure of the semiconductor device due to such corrosion of the copper wire, an ion scavenger is blended in the epoxy resin composition. The purpose of using the ion scavenger is to trap chlorine ions generated when the epoxy resin composition is pressure-molded. However, there is a limit to the capture of chloride ions by the ion scavenger.
Therefore, it is also necessary to use raw materials with low chlorine content, which is a factor that increases the price of raw materials.

  The present invention has been made in view of such circumstances, and is a novel useful as a curing accelerator that can improve the fluidity and curability of the epoxy resin composition and can suppress the chlorine ion concentration in the cured product. An object is to provide a phosphorus compound and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventors have found that a phosphorus compound having a specific structure solves the above problems.
The present invention has been completed based on such findings.

That is, the present invention provides the following [1] to [8].
[1] A phosphorus compound represented by the following general formula (1) or the following general formula (2).

(In the general formula (1), R represents an alkyl group, an aryl group, a divalent or higher organic group, a modified or unmodified phenol novolac type epoxy resin main chain skeleton, a modified or unmodified ortho cresol novolak type epoxy resin main chain. Case, modified or unmodified naphthol orthocresol novolak type epoxy resin main chain skeleton, modified or unmodified bisphenol A type epoxy resin main chain skeleton, modified or unmodified bisphenol F type epoxy resin main chain skeleton, modified or unmodified Dicyclopentadiene type epoxy resin main chain skeleton, modified or unmodified phenol biphenylene alkylene type epoxy resin main chain skeleton, modified or unmodified phenol phenylene alkylene type epoxy resin main chain skeleton, modified or unmodified phenol benzylaldehyde type Epo A main chain skeleton, a group containing a phosphaphenanthrene skeleton, a group in which a part or all of the above group is substituted with bromine, and a part or all of the above main chain skeleton is substituted with bromine X1, X2, and X3 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a carbon number. 1 type selected from 2 to 8 alkenyl groups, l is an integer of 1 or more, and m is an integer of 0 or more.)

(In the general formula (2), Q is one selected from a group having an isocyanurate skeleton, a group having a thiocyanuric acid skeleton, and a group having a melamine skeleton. P is an integer of 1 to 3, q is X1, X2, and X3 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. 1 type selected.)

[2] A method for producing a phosphorus compound as described in [1] above, wherein the phosphine compound represented by the following general formula (3) and an epoxy compound are subjected to an addition reaction.

(In General Formula (3), X1, X2, and X3 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. 1 type selected.)
[3] The method for producing a phosphorus compound according to the above [2], wherein the epoxy compound is a monofunctional epoxy compound.
[4] The method for producing a phosphorus compound according to the above [2], wherein the epoxy compound is a polyfunctional epoxy compound having two or more functions.
[5] The phosphorus according to any one of [2] to [4], wherein the addition reaction between the phosphine compound and the epoxy compound is performed in a molten epoxy compound without using a reaction solvent. Compound production method.
[6] The phosphorus compound according to any one of [2] to [5], wherein the addition reaction between the phosphine compound and the epoxy compound is performed in a molten epoxy compound having a temperature of 130 ° C. or higher and 200 ° C. or lower. Manufacturing method.
[7] The above-mentioned [2], wherein the reaction product obtained by addition reaction of the phosphine compound and the epoxy compound is a mixture of the adduct of the phosphine compound and the epoxy compound and an unreacted epoxy compound. ] The manufacturing method of the phosphorus compound as described in any one of [6].
[8] After completion of the addition reaction between the phosphine compound and the epoxy compound, the reaction product of the phosphine compound and the epoxy compound is rapidly cooled, according to any one of the above [2] to [7]. A method for producing a phosphorus compound.

  According to the present invention, there are provided a novel phosphorus compound useful as a curing accelerator capable of suppressing the chlorine ion concentration in a cured product, and a method for producing the same, by making the epoxy resin composition excellent in fluidity and curability. Can do.

Hereinafter, the present invention will be described in detail.
(Phosphorus compound)
The phosphorus compound of the present invention is represented by the following general formula (1).

  R in the general formula (1) is an alkyl group, an aryl group, a divalent or higher valent organic group, a modified or non-modified phenol novolac type epoxy resin main chain skeleton, a modified or non-modified ortho-cresol novolak type epoxy resin main component. Chain skeleton, modified or unmodified naphthol orthocresol novolac type epoxy resin main chain skeleton, modified or unmodified bisphenol A type epoxy resin main chain skeleton, modified or unmodified bisphenol F type epoxy resin main chain skeleton, modified or unmodified Modified dicyclopentadiene type epoxy resin main chain skeleton, modified or unmodified phenol biphenylene alkylene type epoxy resin main chain skeleton, modified or unmodified phenol phenylene alkylene type epoxy resin main chain skeleton, modified or unmodified phenol benzylaldehyde Type Poxy resin main chain skeleton, group containing phosphaphenanthrene skeleton, group in which part or all of the group is bromine-substituted, and main chain skeleton in which part or all of the main chain skeleton is substituted with bromine One group selected from the group consisting of: X1, X2, and X3 are each independently one selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkenyl group having 2 to 8 carbon atoms. l is an integer of 1 or more, and m is an integer of 0 or more.

The number of carbon atoms of the alkyl group is, for example, preferably 1-14, more preferably 1-10. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, and n-hexyl group. And an isohexyl group.
The alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group or an aryl group.

The number of carbon atoms of the aryl group is, for example, preferably 4-24, and more preferably 4-20. Specific examples of the aryl group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a binaphthyl group, and an anthryl group.
The aryl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkyl group such as a methyl group or an ethyl group, a cycloalkyl group, an alkoxy group or an aralkyl group.

  Examples of the divalent organic group include an alkylene group, a cycloalkylene group, an arylene group, and a polycyclic aromatic group. Among these, a polycyclic aromatic group is preferable from the viewpoint of obtaining the effects of the present invention. These groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkyl group such as a methyl group or an ethyl group, an alkoxy group or an aralkyl group.

  Specific examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group and the like.

  Specific examples of the cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, and a skeleton of sugars such as glucose, lactose, and cellulose.

  Specific examples of the arylene group include a phenylene group, a biphenylene group, and a terphenylene group, and among them, a biphenylene group and a terphenylene group are preferable.

  Examples of the polycyclic aromatic group include a naphthylene group, a binaphthylene group, an anthracenylene group, a pyrenylene group, a triphenylene group, and a fluorenylene group. Among them, a naphthylene group is preferable.

Examples of the trivalent organic group include an alkanetriyl group, a cycle alkanetriyl group, and an arenetriyl group.
Specific examples of the alkanetriyl group include propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group and the like. Specific examples of the cycloalkanetriyl group include cyclopentanetriyl group, cyclohexane A triyl group etc. are mentioned, As a specific example of an arene triyl group, a benzene triyl group, a naphthalene triyl group, etc. are mentioned.
These groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkyl group such as a methyl group or an ethyl group, an alkoxy group or an aralkyl group.

Examples of the tetravalent organic group include an alkanetetrayl group, a cycloalkanetetrayl group, and an arenetetrayl group. Specific examples of the alkanetetrayl group include a butanetetrayl group, a pentanetetrayl group, a hexanetetrayl group, and the like. Specific examples of the cycloalkanetetrayl group include a cyclopentanetetrayl group and a cyclohexanetetrayl group. Specific examples of the arenetetrayl group include a benzenetetrayl group and a naphthalenetetrayl group.
These groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkyl group such as a methyl group or an ethyl group, an alkoxy group or an aralkyl group.

  The main chain skeleton of the epoxy resin described above may be used for R, and the epoxy group may be bonded not only to the end of the main chain but also to the middle of the main chain via an oxygen atom.

Specific examples of the main chain of the epoxy resin include a main chain represented by a portion surrounded by a dotted line in the following formulas (4) to (11).

  In said formula (4)-(11), n is a polymerization degree from which the epoxy equivalent becomes the range of 50-500, More preferably, it is a polymerization degree from which the epoxy equivalent becomes the range of 80-300.

  l is an integer of 1 or more, preferably 2 or more. m is an integer of 0 or more.

In the general formula (1), examples of the alkyl group having 1 to 8 carbon atoms of X1, X2, and X3 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t -Butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-octyl group and the like. Of these, a methyl group, an ethyl group, and a t-butyl group are preferable.
Examples of the alkoxy group having 1 to 8 carbon atoms of X1, X2, and X3 include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, and n-pentyl. An oxy group, n-hexyloxy group, n-octyloxy group, etc. are mentioned. Of these, a methoxy group and an ethoxy group are preferable.
Examples of the alkenyl group having 2 to 8 carbon atoms of X1, X2, and X3 include a vinyl group, a propenyl group, a cyclopropenyl group, a butenyl group, and a cyclobutenyl group. Among these, a vinyl group is preferable.

The phosphorus compound represented by the general formula (1) is preferably at least one selected from phosphorus compounds represented by the following formulas (12) to (27).

Moreover, the phosphorus compound of this invention is represented by following General formula (2).

  Q in the general formula (2) is one selected from a group having an isocyanurate skeleton, a group having a thiocyanuric acid skeleton, and a group having a melamine skeleton. Among these, a group having an isocyanurate skeleton is preferable from the viewpoint of obtaining the effects of the present invention. X1, X2, and X3 are each independently one selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkenyl group having 2 to 8 carbon atoms. The specific examples of X1, X2, and X3 are the same as described above.

  p is an integer of 1 to 3, and q is an integer of 0 to 2.

The phosphorus compound represented by the general formula (2) is preferably at least one selected from phosphorus compounds represented by the following formulas (28) to (30).

  When the phosphorus compound of the present invention is used as a curing accelerator, the fluidity and curability of the epoxy resin composition can be improved. Moreover, the chlorine ion concentration contained in the hardened | cured material of a resin composition can be suppressed.

(Method for producing phosphorus compound)
The method for producing a phosphorus compound of the present invention is characterized in that an addition reaction is performed between a phosphine compound represented by the following general formula (3) (hereinafter also simply referred to as “phosphine compound”) and an epoxy compound.

  In general formula (3), X1, X2, and X3 are each independently selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkenyl group having 2 to 8 carbon atoms. One type. Specific examples of X1, X2, and X3 are the same as described above.

  It does not specifically limit as a monofunctional epoxy compound, A well-known thing can be used. For example, monoglycidyl phenol, glycidyl naphthol, monoglycidyl biphenol, monoglycidyl biphenyl aralkyl, Bis-A (2,2-bis- (4-hydroxy) phenylpropane) monoglycidyl ether, ortho-cresol novolac (OCN) type phenol resin Examples thereof include glycidyl ether, monoglycidyl ether of triphenolalkane, monoglycidyl ether of dicyclopentadiene type phenol resin, monoglycidyl ether of heterocyclic phenol resin, and monoglycidyl ether of alicyclic phenol resin. These may be used alone or in combination of two or more.

  It does not specifically limit as a polyfunctional epoxy compound more than bifunctional, A well-known thing can be used. For example, novolak type epoxy resin, cresol novolak (OCN) type epoxy resin, phenol benzylaldehyde type epoxy resin, aralkyl type epoxy resin, phenol biphenylene alkylene type epoxy resin, phenol phenylene alkylene type epoxy resin, biphenyl skeleton-containing aralkyl type epoxy resin, Biphenyl type epoxy resin, cyclopentadiene type epoxy resin, heterocyclic type epoxy resin, polycyclic aromatic type epoxy resin, naphthalene ring containing epoxy resin, isocyanurate skeleton containing epoxy resin, thiocyanuric acid skeleton containing epoxy resin, melamine skeleton containing epoxy resin Bis-A (2,2-bis- (4-hydroxy) phenylpropane) type epoxy resin, Bis-F (bis- (4-hydroxy) phenylmethane) type epoxy Examples of such resins include alicyclic resins and alicyclic epoxy resins. These epoxy resins may be modified or unmodified. Moreover, 1 type may be used independently and 2 or more types may be used together.

  The epoxy equivalent of the epoxy compound is preferably in the range of 50 to 500, more preferably in the range of 80 to 300, from the viewpoint of curability.

  The addition reaction between the phosphine compound and the epoxy compound is not particularly limited, but the addition reaction is preferably performed in a molten epoxy compound without using a reaction solvent. Specifically, first, the epoxy compound is heated to a melting point or higher and melted. Next, an adduct of a phosphine compound and an epoxy compound is obtained by adding the phosphine compound to the molten epoxy compound and mixing with stirring. Since the reaction solvent is not used in the above reaction, an adduct of the phosphine compound and the epoxy compound, which are the phosphorus compounds of the present invention, can be easily produced without the need for a solvent removal step. Moreover, since the reaction solvent is not used when the phosphorus compound manufactured in this way is used as a hardening accelerator of an epoxy resin composition, generation | occurrence | production of a void (bubble) can be suppressed.

  The temperature during the reaction is preferably 120 to 200 ° C, more preferably 130 to 170 ° C. By making it 120 degreeC or more, the adduct of a phosphine compound and an epoxy compound can be manufactured favorably. By setting the temperature to 200 ° C. or lower, an oxidation reaction of the phosphine compound can be suppressed, and an adduct of the phosphine compound and the epoxy compound can be manufactured favorably.

  Moreover, the said reaction time changes with reaction temperature, the kind of epoxy compound, etc. For example, it may be appropriately adjusted in the range of 3 minutes to 1 hour, preferably 5 to 20 minutes.

  The compounding amount of the phosphine compound can be used in any proportion as long as it is less than or equal to the compounding amount of the epoxy compound, but it is 0.2 to 1.0 times in molar ratio to the epoxy group equivalent of the epoxy compound. It is preferable that the ratio is 0.25 to 0.95 times. If it is in the said range, an unreacted phosphine compound will not remain, and when the epoxy resin composition is shape | molded, the raise of the melt viscosity of a composition can be suppressed. On the other hand, within the said range, a part of epoxy compound will remain unreacted. Thus, the reaction product obtained by addition reaction of a phosphine compound and an epoxy compound may be an adduct of a phosphine compound and an epoxy compound and a mixture of unreacted epoxy compounds.

After completion of the addition reaction between the phosphine compound and the epoxy compound, it is preferable to quench the reaction product of the phosphine compound and the epoxy compound. By effectively removing heat after completion of the reaction, an adduct of the phosphine compound and the epoxy compound can be produced satisfactorily.
The means for rapidly cooling the reaction product is not particularly limited, and examples thereof include a method of pouring the reaction product onto a Teflon sheet or a stainless steel vat.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples.

Example 1
In a 500 mL beaker, 3.52 g of 9,9-bis (4-glycoxyphenyl) fluorene (epoxy equivalent 260, manufactured by Osaka Gas Chemical Co., Ltd.) was added and heated to 160 ° C. to be melted. Then, 2.00 g of triphenylphosphine (made by Hokuko Chemical Co., Ltd.) was added. After stirring for 10 minutes to obtain a uniform liquid, the mixture was poured onto a Teflon sheet and rapidly cooled and solidified. 5.12 g of a reaction product of triphenylphosphine and 9,9-bis (4-glycoxyphenyl) fluorene was obtained. About the obtained reaction product, NMR and mass spectrometry were performed and the structure was confirmed.

From the above results, the obtained reaction product is a mixture of two types of phosphorus compounds represented by the following formulas (12) and (13) and 9,9-bis (4-glycoxyphenyl) fluorene. I was able to confirm. Moreover, the yield of the two types of phosphorus compounds represented by the formulas (12) and (13) was 93%.

(Example 2)
75.76 g of a reaction product was obtained in the same manner as in Example 1 except that 66.16 g of 9,9-bis (4-glycoxyphenyl) fluorene was changed to 24.99 g of triphenylphosphine. When the obtained reaction product was subjected to NMR and mass spectrometry, two types of phosphorus compounds represented by formulas (12) and (13), 9,9-bis (4-glycoxyphenyl) fluorene, It was confirmed that the mixture was. The yield of the two types of phosphorus compounds represented by formulas (12) and (13) was 83%.

(Example 3)
107 g of a reaction product was obtained in the same manner as in Example 1 except that 88.18 g of 9,9-bis (4-glycoxyphenyl) fluorene and 88.18 g of triphenylphosphine were changed. When the obtained reaction product was subjected to NMR and mass spectrometry, two types of phosphorus compounds represented by formulas (12) and (13), 9,9-bis (4-glycoxyphenyl) fluorene, It was confirmed that the mixture was. The yield of the two types of phosphorus compounds represented by formulas (12) and (13) was 95%.

Example 4
180 g of a reaction product was obtained in the same manner as in Example 1 except that 176.37 g of 9,9-bis (4-glycoxyphenyl) fluorene was changed to 25.05 g of triphenylphosphine. When the obtained reaction product was subjected to NMR and mass spectrometry, two types of phosphorus compounds represented by formulas (12) and (13), 9,9-bis (4-glycoxyphenyl) fluorene, It was confirmed that the mixture was. The yield of the two types of phosphorus compounds represented by formulas (12) and (13) was 89%.

(Example 5)
In a 500 mL beaker, 79.50 g of YX-4000K (epoxy equivalent 192, manufactured by Mitsubishi Chemical Corporation) was charged and heated to 140 ° C. to melt. Next, 30.02 g of triphenylphosphine (made by Hokuko Chemical Co., Ltd.) was added. After stirring for 10 minutes to obtain a uniform liquid, the mixture was poured onto a Teflon sheet and rapidly cooled and solidified. 106 g of a reaction product of triphenylphosphine and YX-4000K was obtained. About the obtained reaction product, NMR and mass spectrometry were performed and the structure was confirmed.

From the above results, it was confirmed that the obtained reaction product was a mixture of two types of phosphorus compounds represented by the following formulas (14) and (15) and YX-4000K. The yield of the two types of phosphorus compounds represented by formulas (14) and (15) was 97%.

(Example 6)
55.17 g of a reaction product was obtained in the same manner as in Example 5 except that 23.99 g of YX-4000K and 32.79 g of triphenylphosphine were used. When the obtained reaction product was subjected to NMR and mass spectrometry, it was confirmed to be a phosphorus compound represented by the formula (15). The yield of the phosphorus compound represented by the formula (15) was 97%.

(Example 7)
In a 100 mL beaker, 2.65 g of CNE-200ELF-80 (epoxy equivalent 198, manufactured by Changchun Artificial Resin Co., Ltd.) was added and heated to 140 ° C. to melt. Subsequently, 1.01 g of triphenylphosphine (made by Hokuko Chemical Co., Ltd.) was added. After stirring for 10 minutes to obtain a uniform liquid, the mixture was poured onto a Teflon sheet and rapidly cooled and solidified. 3.04 g of a reaction product of triphenylphosphine and CNE-200ELF-80 was obtained. About the obtained reaction product, NMR and mass spectrometry were performed and the structure was confirmed.

From the above results, it was confirmed that the obtained reaction product was a phosphorus compound represented by the following formula (21). The yield of the phosphorus compound represented by formula (21) was 83%.

(Example 8)
In a 500 mL beaker, 10.00 g of TEPIC (triglycidyl isocyanurate) (epoxy equivalent 100, manufactured by Nissan Chemical Industries, Ltd.) was charged and heated to 140 ° C. to melt. Next, 26.26 g of triphenylphosphine (made by Hokuko Chemical Co., Ltd.) was added. After stirring for 10 minutes to obtain a uniform liquid, the mixture was poured onto a Teflon sheet and rapidly cooled and solidified. 34.64 g of a reaction product of triphenylphosphine and triglycidyl isocyanurate was obtained. About the obtained reaction product, NMR and mass spectrometry were performed and the structure was confirmed.

From the above results, it was confirmed that the obtained reaction product was a phosphorus compound represented by the following formulas (28) to (30). The yield of the phosphorus compound represented by the formulas (28) to (30) was 96%.

Example 9
In a 500 mL beaker, 36.33 g of YX-4000K (epoxy equivalent 192, manufactured by Mitsubishi Chemical Corporation) was charged and heated to 140 ° C. to melt. Next, 13.74 g of tri (paratolyl) phosphine (manufactured by Hokuko Chemical Co., Ltd.) was added. After stirring for 10 minutes to obtain a uniform liquid, the mixture was poured onto a Teflon sheet and rapidly cooled and solidified. 48.72 g of a reaction product of tri (paratolyl) phosphine and YX-4000K was obtained. About the obtained reaction product, NMR and mass spectrometry were performed and the structure was confirmed.

From the above results, it was confirmed that the obtained reaction product was a phosphorus compound represented by the following formulas (16) and (17). The yield of the phosphorus compound represented by the formulas (16) and (17) was 97%.

(Example 10)
In a 500 mL beaker, 36.30 g of YX-4000K (epoxy equivalent 192, manufactured by Mitsubishi Chemical Corporation) was charged and heated to 140 ° C. to melt. Next, 13.72 g of tri (ortho-tolyl) phosphine (made by Hokuko Chemical Co., Ltd.) was added. After stirring for 10 minutes to obtain a uniform liquid, the mixture was poured onto a Teflon sheet and rapidly cooled and solidified. 48.67 g of a reaction product of tri (orthotolyl) phosphine and YX-4000K was obtained. About the obtained reaction product, NMR and mass spectrometry were performed and the structure was confirmed.

From the above results, it was confirmed that the obtained reaction product was a phosphorus compound represented by the following formulas (31) and (32). The yield of the phosphorus compound represented by the formulas (31) and (32) was 97%.

(Example 11)
In a 500 mL beaker, 36.32 g of YX-4000K (epoxy equivalent 192, manufactured by Mitsubishi Chemical Corporation) was charged and heated to 140 ° C. to melt. Next, 13.71 g of tri (paramethoxyphenyl) phosphine (Hokuko Chemical Co., Ltd.) was added. After stirring for 10 minutes to obtain a uniform liquid, the mixture was poured onto a Teflon sheet and rapidly cooled and solidified. 48.68 g of a reaction product of tri (paramethoxyphenyl) phosphine and YX-4000K was obtained. About the obtained reaction product, NMR and mass spectrometry were performed and the structure was confirmed.

From the above results, it was confirmed that the obtained reaction product was a phosphorus compound represented by the following formulas (18) and (19). The yield of the phosphorus compound represented by the formulas (18) and (19) was 97%.

(Examples 12 to 18 and Comparative Example 1)
The components of the types and blending amounts shown in Table 1 were kneaded by biaxial kneading under conditions of a kneading temperature of 80 to 90 ° C., a kneading time of 20 minutes and a rotation speed of 130 rpm, to prepare an epoxy resin composition. In Table 1, blanks indicate no blending.

The detail of each component of Table 1 used for preparation of an epoxy resin composition is as follows.
[Component (A)] YX-4000K: Epoxy resin (biphenyl type epoxy resin), manufactured by Mitsubishi Chemical Corporation, trade name, epoxy equivalent 195
[Component (B)] MEH-7500: curing agent (triphenylmethane type phenol resin), manufactured by Meiwa Kasei Co., Ltd., trade name, hydroxyl group equivalent 97
[Component (C)] Inorganic filler (fused silica), manufactured by Denki Kagaku Kogyo Co., Ltd.
[Component (D)]
Curing accelerator (1): Phosphorus compound produced in Example (2) Curing accelerator (2): Phosphorus compound produced in Example (5) Curing accelerator (3): In Example (6) Phosphorus compound / curing accelerator (4) produced: Phosphorus compound / curing accelerator produced in Example (8) (5): Phosphorus compound / curing accelerator produced in Example (9) (6): Example Phosphorus compound / curing accelerator (7) produced in (10): Phosphorus compound / curing accelerator produced in Example (11) (8): Triphenylphosphine (manufactured by Hokuko Chemical Co., Ltd.)
[(E) component] Coupling agent (manufactured by JNC Corporation)
[Component (F)] Colorant: Carbon black (Mitsubishi Chemical Corporation)
[Component (G)] Mold release agent: Carnauba wax (manufactured by Toyo Adre Co., Ltd.)

Under the measurement conditions shown below, the properties of the epoxy resin compositions prepared in Examples 12 to 18 and Comparative Example 1 were measured and evaluated. The results are shown in Table 1.
<Evaluation items>
(1) Spiral flow The flow distance (cm) of the epoxy resin composition was measured under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 120 seconds.
(2) Time for the shear strength to reach 3 N · m (curing time)
Using the epoxy resin composition, tablets having a diameter of 25 to 28 mm were molded at a load of 190 kg and at room temperature. Using a curast meter (trade name: Curast Meter 7 manufactured by JSR Trading Co., Ltd.), the torque (N · m) change applied to the tablet was measured at a temperature of 175 ° C. for 5 minutes, and the shear strength became 3 N · m. The time to reach was measured. The measurement conditions were a frequency of 100 cpm and a load cell 200N.
(3) Chlorine ion concentration An epoxy resin composition is injected into a molding machine and cured under conditions of a mold temperature of 175 ° C., a molding pressure of 80 kg / cm ² and a curing time of 2 minutes, and further a mold temperature of 175 ° C. and a curing time of 8 A test piece obtained by post-curing under conditions of time was pulverized. The crushed sample was extracted with hot water, and the chloride ion concentration was analyzed with an ion chromatograph analyzer (manufactured by Thermo SCIENTIFIC, trade name: ICS-1100).

In addition, the compounding quantity of hardening accelerator (1)-(7) in Table 1 is a triphenylphosphine conversion value.

  In Examples 12 to 18 using the phosphorus compound of the present invention as a curing accelerator, the epoxy resin composition was excellent in fluidity and curability, and the chlorine ion concentration in the cured product was as low as 2.8 to 11.3 ppm. It became.

  When the phosphorus compound of the present invention is used as a curing accelerator, the fluidity and curability of the epoxy resin composition are improved, and the chlorine ion concentration in the resin composition can be suppressed. Can be suitably used.

Claims (8)

The phosphorus compound represented by the following general formula (1) or the following general formula (2).

(In the general formula (1), R represents an alkyl group, an aryl group, a divalent or higher organic group, a modified or unmodified phenol novolac type epoxy resin main chain skeleton, a modified or unmodified ortho cresol novolak type epoxy resin main chain. Case, modified or unmodified naphthol orthocresol novolak type epoxy resin main chain skeleton, modified or unmodified bisphenol A type epoxy resin main chain skeleton, modified or unmodified bisphenol F type epoxy resin main chain skeleton, modified or unmodified Dicyclopentadiene type epoxy resin main chain skeleton, modified or unmodified phenol biphenylene alkylene type epoxy resin main chain skeleton, modified or unmodified phenol phenylene alkylene type epoxy resin main chain skeleton, modified or unmodified phenol benzylaldehyde type Epo A main chain skeleton, a group containing a phosphaphenanthrene skeleton, a group in which a part or all of the above group is substituted with bromine, and a part or all of the above main chain skeleton is substituted with bromine X1, X2, and X3 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a carbon number. 1 type selected from 2 to 8 alkenyl groups, l is an integer of 1 or more, and m is an integer of 0 or more.)

(In the general formula (2), Q is one selected from a group having an isocyanurate skeleton, a group having a thiocyanuric acid skeleton, and a group having a melamine skeleton. P is an integer of 1 to 3, q is X1, X2, and X3 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. 1 type selected.) It is a manufacturing method of the phosphorus compound according to claim 1,
A method for producing a phosphorus compound, in which a phosphine compound represented by the following general formula (3) and an epoxy compound are subjected to an addition reaction.

(In General Formula (3), X1, X2, and X3 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. 1 type selected.)   The method for producing a phosphorus compound according to claim 2, wherein the epoxy compound is a monofunctional epoxy compound.   The manufacturing method of the phosphorus compound of Claim 2 whose said epoxy compound is a polyfunctional epoxy compound more than bifunctional.   The method for producing a phosphorus compound according to any one of claims 2 to 4, wherein the addition reaction between the phosphine compound and the epoxy compound is carried out in a molten epoxy compound without using a reaction solvent.   The method for producing a phosphorus compound according to any one of claims 2 to 5, wherein the addition reaction between the phosphine compound and the epoxy compound is performed in a molten epoxy compound having a temperature of 130 ° C or higher and 200 ° C or lower.   The reaction product obtained by addition reaction of the phosphine compound and the epoxy compound is an adduct of the phosphine compound and the epoxy compound, and a mixture of unreacted epoxy compounds. The manufacturing method of the phosphorus compound as described in any one.   The method for producing a phosphorus compound according to any one of claims 2 to 7, wherein after the addition reaction between the phosphine compound and the epoxy compound is completed, a reaction product of the phosphine compound and the epoxy compound is quenched. .