JP2000191673A - New phosphoric acid ester and mold releasing agent comprising the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound superior to a conventional mold releasing agent in transparency and mold releasing property, and useful as a mold releasing agent which is used to produce a transparent resin such as a plastic lens. SOLUTION: A compound of formula I (m=1,2; n=2,3; R1 is a 1-20C residual group excluding phenyl; R2 and R3 are each H, methyl or ethyl, but the case where both of them are H is excluded), e.g. mono(1-(1-n-butoxy-2-propoxy)-2- propyl) phosphate. A compound of formula I is obtained by hydrolyzing a compound of formula II (X is a halogen) [e.g. mono(1-(1-n-butoxy-2-propoxy)-2-propyl) phosphoric acid dichloride] preferably at a pH of <=7, preferably at a temp. of 30-70 deg.C. A compound of formula II is obtained, for example, by reacting an oxyalcohol such as 1-(1-n-butoxy-2-propoxy)-2-propanol with a phosphorous oxyhalide such as phosphorous oxychloride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phosphoric ester useful as a mold release agent, a method for producing the same, and a transparent resin, a transparent optical material, and a plastic lens containing the phosphoric ester.

[0002]

2. Description of the Related Art A transparent resin generally has a transparency comparable to that of glass and a higher impact strength than glass. For example, a window glass for an aircraft, a headlight cover for an automobile,
It is used in fields such as drinking water containers, sealants, liquid crystal panels, optical disks, optical fibers, and plastic lenses.

[0003] Types of general transparent resins include olefin resins such as polyvinyl chloride, polypropylene, PMMA, and (meth) acrylic resins, polyene-polythiol resins, polyester resins, polycarbonate resins, epoxy resins, and polyurethane resins. Can be Usually, these transparent resins are molded by injection molding or cast polymerization. In either case, a product cannot be obtained unless the resin is released from the mold.

However, when such resins are molded without a mold release agent, excessive stress is applied at the time of mold release.
In many cases, undesirable results such as deformation of the molded product, such as warpage, and generation of optical distortion inside, are given.

[0005] Further, epoxy resin and urethane resin are
As can be seen from the fact that it is also used for adhesives, it is known as an extremely strong resin, and when using a metal or glass mold, the use of a mold release agent is usually essential

The release agent includes an external release agent which is applied to the surface of a molding die by using a spray or the like, and an internal release agent which is previously added to a raw material monomer. As the external release agent, not only the operation is complicated, but also there is a problem that the release film is difficult to be constant and the surface accuracy is reduced. Therefore, the internal release agent is preferably used.

[0007] As these internal release agents, conventionally known compounds include aliphatic alcohols, fatty acid esters, triglycerides, fluorinated surfactants, metal salts of higher fatty acids, and the like. There are drawbacks such as difficulty in releasing from the mold, turbidity inside the resin and on the surface, and easily impairing the original transparency of the resin.

[0008] Impairing transparency is a problem especially in a molded article made of a transparent resin utilizing high transparency. Among them, a plastic lens which can be out of spec even with a slight cloudiness which cannot be judged by ordinary eyes. In the field of optical materials typified by, there has been a very fatal drawback.

Various proposals have been made to solve this problem. For example, a method using an alkoxyalkyl phosphate (Japanese Patent Publication No. 6-20754,
JP-A-3-287641), a method using a phosphinic ester (JP-A-58-49747), and the like. The present inventors have also proposed a method using an acid phosphate (Japanese Patent Publication No. 7-77733), a method using a thiophosphate (Japanese Patent Application Laid-Open No. 5-306320),
A method using an acidic phosphonic acid derivative (JP-A-8-578)
No. 64 gazette).

However, even if these methods are used,
Transparency is still strictly insufficient or colored,
If the release agent itself has a high viscosity, it is difficult to use, has an unpleasant odor, and in the case of a resin with extremely strong adhesive strength, the usual amount of the release agent is not good or the release property is improved. There is a problem that the resin becomes cloudy when a large amount of the release agent is used. In addition, even with a release agent that has cleared coloring, release properties, transparency, etc., the range in which it can be used in terms of quality is extremely narrow. In some cases, it was necessary to select a suitable lot. Furthermore, problems may occur during secondary processing, such as uneven dyeing and reduced adhesion of the hard coat. Usually, better results are often obtained with the use of acidic phosphonic acid derivatives. However, when this acidic phosphonic acid derivative is used in a special method for uniformly and urethane polymerization in a short time by using a Lewis acid and a tertiary amine in combination (Japanese Patent Application Laid-Open No. 8-208792),
Transparency tends to be impaired, and it has been difficult to say that conventional methods are sufficiently satisfactory.

[0011]

That is, an object of the present invention is to provide a release agent which is more excellent in transparency and releasability than a conventional release agent, and a high-quality release agent which is excellent in transparency. It is to provide a transparent resin.

[0012]

Means for Solving the Problems In view of the above problems, the present inventors have conducted intensive studies, and as a result, have found a novel compound, a phosphoric ester, and used the phosphoric ester and its composition as a releasing agent for a transparent resin. Using the above, the above problem was solved, a high-quality transparent resin was found to be obtained, and the present invention was reached.

That is, the present invention provides the following formula (1)

Embedded image (In the formula, m represents 1 or 2, n represents an integer of 2 to 3, R ₁ represents a residue having 1 to 20 carbon atoms excluding a phenyl group, and R ₂ and R ₃ each represent a hydrogen atom , A methyl group and an ethyl group, except that both R ₂ and R ₃ are hydrogen atoms), a method for producing the same, a releasing agent containing the phosphoric ester, and a phosphoric ester. The transparent resin contained and the transparent resin are made of a transparent optical material and a plastic lens.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The phosphoric acid ester of the formula (1) of the present invention is a phosphoric acid monoester or a phosphoric acid diester having an alkylethylene glycol skeleton, wherein m is 1 or 2.

N in the formula (1) represents the number of repetitions of the alkylethylene glycol skeleton, and is in the range of 2-3.
When n is 1, uneven releasability may occur depending on the shape of the mold, and when n is 4 or more, it may be difficult to synthesize the raw materials or the cost may be increased.

R ₂ and R ₃ in the formula (1) represent hydrogen, a methyl group or an ethyl group (except when both R ₂ and R ₃ are hydrogen). When both R ₂ and R ₃ are hydrogen, the releasability is reduced as compared with the phosphate of the present invention in which at least one of them is substituted with a methyl group or an ethyl group.

The R ₁ residue represented by the formula (1) is an alkyl residue having 1 to 20 carbon atoms excluding a phenyl group. Phenyl groups can cause the resin to color. If the number of carbon atoms exceeds 20, transparency may decrease. Preferably it is in the range of 3 to 15.

The residue represented by R ₁ must have at least 1 to 20 carbon atoms, except for the phenyl group. Therefore, typical forms of the residues will be described below, but the present invention is not limited to these forms. Examples of the form of the residue include a linear saturated alkyl group, a linear unsaturated alkyl group, a branched saturated alkyl group, a branched unsaturated alkyl group, a linear saturated alkylaryl group, and a linear unsaturated alkyl group. Examples thereof include an alkylaryl group, an arylalkyl group, an arylalkylene group, and an alkylarylalkylene group. In addition, there is no problem with heteroatoms and heterostructures such as an ether bond, a thioether bond, a sulfoxy bond, a sulfone bond, an ester bond, a carbonyl bond, an amide bond, an imide bond, a hetero ring, and a cycloalkylene group ring in the residue. It may be included in the range. Further, some of the hydrogen atoms constituting these residues may be replaced with halogen atoms such as fluorine, chlorine, and bromine as far as no problem occurs.

The phosphoric ester of the formula (1) of the present invention is synthesized, for example, by the following method. Epoxy compounds such as 1,2-propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, and 3,4-epoxyhexane, and alcohols and hydroxy compounds represented by phenols other than phenol By reacting an oxyalcohol obtained by the reaction with a phosphorus oxyhalide, the following formula (2)

Embedded image (In the formula, m represents 1 or 2, n represents an integer of 2 to 3, R ₁ represents a residue having 1 to 20 carbon atoms excluding a phenyl group, and R ₂ and R ₃ each represent a hydrogen atom , A methyl group and an ethyl group, provided that R ₂ and R ₃ are not both hydrogen atoms, and X represents a halogen atom.) Obtained by When hydrolysis is performed at PH = 8 or less,
Gives favorable results.

When it is desired to selectively synthesize a diester (m = 2), a phosphorus trihalide such as phosphorus trichloride is reacted with an oxyalcohol instead of phosphorus oxyhalide to obtain a phosphorous diester. Synthesize the body. Next, by-produced oxyhalogenide is distilled off and removed from the system by a purification operation such as distillation under reduced pressure, and then reacted with halogens such as chlorine to produce a halogenophosphorous diester. It is obtained by hydrolysis in the same manner as when used. R _{1 to} R ₃ in the general formula (2),
The meanings of n and m are the same as those in the general formula (1).

Hereinafter, the production method of each step will be described with reference to a specific example.

Embedded image

The 1-butanol of the formula (A), which is an alcohol, is reacted with the 1,2-propylene oxide of the formula (B) to synthesize 1-butoxy-2-propanol of the formula (C). By reacting 1,2-propylene oxide of B), 1- (1-butoxy-2-propoxy) -2-propanol of the formula (D), which is an oxyalcohol, is synthesized. The reaction temperature of the addition reaction for synthesizing the oxyalcohols varies considerably depending on, for example, the difference in acidity such as whether the hydroxy group is alcoholic or phenolic, and is preferably 0 to 200 ° C.
30-150 ° C is particularly preferred.

For the purpose of improving the reaction rate, a base such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, triethylamine, pyridine or the like may be added as a catalyst. The addition amount is 0.001 to the reaction solution.
The range is preferably from 5 to 5% by weight, and more preferably from 0.05 to 3% by weight.

The reaction solvent may not be used, but when used, an aprotic solvent such as acetonitrile, toluene, dichloroethane, chlorobenzene, dimethylformamide and the like is preferable. Raw material 1-butanol, 1-butoxy-2-propanol, and / or 1,2-propylene oxide may be added dropwise for the purpose of improving selectivity and suppressing a rapid increase in internal temperature. The thus obtained 1- (1-butoxy-2-propoxy) -2-propanol of the formula (D) may be used in the next reaction as it is, but is usually often purified by distillation.

The formula (F) mono (1- (1-butoxy-) which belongs to the phosphate halides of the formula (2) according to the present invention.
2-propoxy) -2-propyl) phosphoric dihalide is
1- (1-butoxy-2-propoxy) -2 of the formula (D)
-Propanol is obtained by reacting with phosphorus oxyhalide of the formula (E) represented by phosphorus oxychloride, phosphorus oxybromide and the like. Among the phosphorus oxyhalides, economically advantageous phosphorus oxychloride is preferably used.

The molar ratio of 1- (1-butoxy-2-propoxy) -2-propanol of formula (D) to phosphorus oxyhalides of formula (E) is largely determined by the desired composition of the phosphate ester. But preferably 0.5 to 2.5
(D / E), particularly preferably 0.9 to 2.1 (D / E).
It is.

The reaction temperature is preferably from 0 to 100 ° C., preferably from 10 to 100 ° C.
It is more preferable that the temperature is from 50 ° C to 50 ° C. If it exceeds 100 ° C., it may be markedly colored.

For the purpose of improving the reaction rate, bases such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, triethylamine, pyridine and the like may be added as a hydrogen halide catching agent. In particular, when a tertiary amine such as triethylamine or pyridine is used, preferable results are obtained. The amount of the base used is 0.1 to the hydroxy group of 1- (1-butoxy-2-propoxy) -2-propanol of the formula (D) which is an oxy alcohol.
Preferably 5 to 2.0 equivalents, more preferably 0.9 to 1.5 equivalents.

When no base is used, it is preferable not to use a reaction solvent. When a base is used, it is often convenient to use a reaction solvent.For example, a solvent that separates from water such as benzene, toluene, dichloroethane, chlorobenzene, dichlorobenzene, butyl acetate, and methyl isobutyl ketone is preferably used. Can be Of these, halogen solvents such as dichloroethane, chlorobenzene, and dichlorobenzene are more preferable.

For the purpose of improving selectivity and suppressing a rapid rise in internal temperature, oxyalcohols of the formula (D) 1-
(1-butoxy-2-propoxy) -2-propanol and a base are simultaneously added dropwise, or phosphorus oxyhalides, 1- (1-butoxy-2-propoxy) -2-propanol, and all three kinds of bases are used. It may be dropped at the same time.

The mono (1- (1-butoxy-2-propoxy) -2-propyl) phosphoric acid of the formula (G) belonging to the phosphoric ester of the formula (1) according to the present invention is represented by the formula (F):
It is obtained by hydrolyzing (1-butoxy-2-propoxy) -2-propyl) phosphoric dihalide.

Hydrolysis includes aqueous sodium hydroxide, aqueous sodium carbonate, aqueous sodium hydrogen carbonate, aqueous potassium hydroxide, aqueous potassium carbonate, aqueous sodium phosphate, aqueous sodium acetate, aqueous ammonia, water, aqueous acetic acid, hydrochloric acid, sulfuric acid, and the like. Although various bases and acids can be used, the pH of the hydrolysis is 8 or less,
Particularly, it is preferably 7 or less. Even if the hydrolysis is carried out in a state where the pH exceeds 8, a satisfactory release agent performance can be obtained, but the obtained product tends to be colored and side reactions other than hydrolysis occur. There is. As the type of hydrolyzing agent, from the viewpoint of economy, quality, and operability,
Water is preferred. Further, it is often the case that the hydrolysis is carried out while bubbling the reaction solution with nitrogen to give a preferable result.

The reaction temperature is preferably from 0 to 100 ° C.,
It is more preferable that the temperature is 70 ° C. In the case of hydrolysis,
For the purpose of suppressing a rapid increase in the internal temperature, for example, a hydrolyzing agent such as water is added to a mono (1- (1-butoxy-2-)-formula (F).
A form in which propoxy) -2-propyl) phosphoric acid dihalide or a reaction solution thereof is added dropwise often gives more favorable results.

The reaction liquid thus obtained is purified, if necessary, by an adsorption treatment typified by washing, filtration, activated carbon treatment and the like, and a distillation operation such as desolvation. -(1-butoxy-2-propoxy)
-2-propyl) phosphoric acid is obtained.

Alternatively, the phosphoric ester of formula (1) according to the present invention can be obtained by reacting hydroxy compounds with diphosphorus pentoxide.

Examples of the phosphoric acid ester of the present invention including the formula (G) include the following compounds. Representative compounds include, for example, (mono, di) (1- (1-methoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di)
Di) (1- (1-ethoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-propoxy-
2-propoxy) -2-propyl) phosphoric acid, (mono, di)
(1- (1-butoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-hexyloxy-2)
-Propoxy) -2-propyl) phosphoric acid, (mono, di)
(1- (1-octyloxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-nonyloxy-
2-propoxy) -2-propyl) phosphoric acid, (mono, di)
(1- (1-decaloxy-2-propoxy) -2-propyl) phosphoric acid, (1- (1-dodecanoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-
Tetradecaloxy-2-propoxy) -2-propyl)
Phosphoric acid, (mono, di) (1- (1-hexadecaloxy-2)
-Propoxy) -2-propyl) phosphoric acid, (mono, di)
(1- (1-stearoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-eicosaloxy-2-propoxy) -2-propyl) phosphoric acid, (mono,
Di) (1- (1-benzyloxy-2-propoxy) -2
-Propyl) phosphoric acid, (mono, di) (1- (1-butylphenoxy-2-propoxy) -2-propyl) phosphoric acid,
(Mono, di) (1- (1-hexylphenoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1-
(1-octylphenoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-nonylphenoxy-2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1-butoxy-2-butyroxy) -2
-Butyl) phosphoric acid, (mono, di) (2- (2-butoxy-
3-butyroxy) -3-butyl) phosphoric acid, (mono, di)
(1- (1-nonylphenoxy-2-butyroxy) -2
-Butyl) phosphoric acid, (mono, di) (2- (2-nonylphenoxy-3-butyroxy) -3-butyl) phosphoric acid, (mono, di) (1- (1- (1-methoxy-2-propoxy)) -2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1- (1-propoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid, (mono, di) ( 1- (1- (1-butoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1- (1-hexyloxy-2-propoxy) -2-propoxy) ) -2-Propyl) phosphoric acid, (mono, di) (1- (1- (1-octyloxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1 -(1-nonyloxy-2-propoxy) -2-propoxy) -2- (Ropyl) phosphoric acid, (mono, di) (1- (1- (1-stearoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid, (mono, di) (1- (1- (1- Nonylphenoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid,
(Mono, di) (1- (1- (1-butoxy-2-butoxy) -2-butoxy) -2-butyl) phosphoric acid, (mono, di) (2- (2- (2-butoxy-3-) Butyroxy) -3-butyroxy) -3-butyl) phosphoric acid, (mono,
Di) (1- (1- (1-nonylphenoxy-2-butyroxy) -2-butyroxy) -2-butyl) phosphoric acid, (mono, di) (2- (2- (2-nonylphenoxy-3-butyroxy) ) -3-butyroxy) -3-butyl) phosphoric acid and the like, as well as a fluorine-substituted or chlorine-substituted product of these phosphates,
Halogen-substituted products such as bromine-substituted products are also included. The phosphate ester of the present invention is not limited only to these listed compounds.

The release agent of the present invention is a phosphoric ester composition essentially including at least the phosphoric ester represented by the formula (1). For example, in addition to the phosphoric ester represented by the formula (1), a triester, a phosphoric acid, a hydroxy compound, water, a metal, a metal salt, an organic metal salt, other phosphoric esters, and the like are included as long as there is no problem. In addition, for the purpose of lowering viscosity to improve operability and dispersibility, and increasing solubility in monomers and polymers, for example, hydrocarbon solvents represented by hexane and the like, alkyl (allyl) alcohol And alkoxy (allyloxy) alkyl (allyl) alcohols and their ethers and esters, benzene derivatives represented by toluene, xylene, etc., halogen solvents such as dichloromethane, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, acetone, methyl ethyl ketone, Tetrahydrofuran, N, N-dimethylform Amide, N, at all no problem include with no range problem similarly like aprotic polar solvents represented by · N-dimethyl-imidazolidinone.

The release agent of the present invention may be used in the form of an internal release agent which is previously added to a monomer or an external release agent which is previously applied to a molding die. A mold system is preferably used.

The transparent resin of the present invention is a transparent resin containing an organic compound as a main component, for example, olefin resin, epoxy resin, urethane resin, carbonate resin, ester resin, olefin-thiol resin, epoxy-thiol resin, and These include transparent resins used in combination, but the present invention is not limited to only the resins listed above, but is particularly effective in the case of polythiourethane resins.

The release agent of the present invention is used, for example, as follows. The molding modes are roughly classified into approximately three types: an injection molding method, an injection cure method, and a casting polymerization method. Operations performed for all three types will be described first.

The phosphoric ester or the release agent of the present invention is added to the raw material monomer, oligomer, or polymer pellet, and if necessary, mixed and dissolved by heating. The amount of the release agent varies greatly depending on the raw material and cannot be limited, but is generally about 0.0001 to 30% by weight. Next, if necessary, defoaming is performed by an appropriate method such as decompression, and the resulting mixture is poured into a molding die and cured to take out a transparent resin molded product. The obtained transparent resin is usually annealed at a temperature of about 100 ° C. or higher for the purpose of removing distortion and completing polymerization more completely. Hereinafter, each of the above-described three embodiments will be briefly described individually.

In the case of injection molding often used in the case of olefin, polycarbonate, polyester resin, etc.,
After adding a release agent to the pellets and heating and dissolving them at about 100 to 400 ° C., the molten liquid is poured into a metal mold mainly and cooled to harden the transparent resin.

In the case of the injection cure method often used for some urethane resins and epoxy resins,
A metal mold is mainly used, a mold release agent, a curing agent, etc. are added to the monomer composition, defoaming is performed under reduced pressure, etc., and then immediately injected into the mold before the resin is cured, followed by thermosetting. Let it.

Casting polymerization often used for precision molding of most resins including urethane and olefin resins is as follows:
After adding a release agent to the monomer composition and defoaming by decompression etc., the defoaming liquid is poured into a glass mold consisting mainly of a glass mold and a resin gasket or tape, and polymerized by heat or radiation Let it cure. In the case of heat polymerization, the temperature is gradually raised from a low temperature to a high temperature in a temperature range of about 0 to 200 ° C., and the polymerization is completed in about 1 to 100 hours. In the case of radiation polymerization, ultraviolet rays of 400 nm or less are mainly used. The amount of UV light is about 1-100
In many cases, irradiation is performed at an intensity of 0 mJ / sec for 1 to 7200 sec, and sometimes cooling or irradiation is performed several times before irradiation in order to remove heat or obtain a molded product having optical uniformity. In some cases, thermal polymerization and radiation polymerization are combined. The present invention provides, in this casting polymerization,
Be more effective.

In the above molding method, a thermal catalyst, a photocatalyst,
Organic compounds and inorganic compounds other than raw materials such as UV absorbers, antioxidants, polymerization inhibitors, oil-soluble dyes, fillers, plasticizers, other release agents, and solvents can be added within a range without any problem.

Further, the obtained transparent resin, transparent optical material,
In addition, plastic lenses have surface polishing, antistatic treatment, hard coating, etc. to improve anti-reflection, high hardness, abrasion resistance, chemical resistance, anti-fog, or fashion, if necessary. Physical or chemical treatment such as treatment, anti-reflection coating treatment, and light control treatment can be performed.

[0047]

The present invention will be described below in more detail with reference to examples and comparative examples. The refractive index, Abbe number, degree of coloring, transparency, releasability, and surface state of the obtained transparent resin were evaluated by the following test methods.

Refractive index, Abbe number: Measured at 20 ° C. using a Pulfrich refractometer. Coloring degree: A 9 mm flat plate was prepared and YI was measured with a Minolta colorimeter, and 4.5 or less was evaluated as (○) and 4.5 or more as (X). Transparency; 9mm thick, Φ75mm circular plate is made,
The measurement was performed with a gray-scale image device. C: A value of 50 or less in average brightness was evaluated as (○), and a product exceeding 50 was evaluated as (x). Releasability: evaluated using a glass mold having an outer diameter of 84 mm and a height of 17 mm, an outer diameter of 84 mm and a height of 11 mm, and a convex mold made of tape. After charging 5 sets each, after the polymerization is completed, it is allowed to cool to room temperature,
A case where three or more sheets were naturally released from the mold was rated as (○), and a case where three or more sheets required excessive force, or the case where the glass mold was broken or peeled was rated as (x).

Example 1 (Synthesis of Phosphoric Ester-1) 600.0 g of phosphorus oxychloride (3.
91 mol) and 1000 ml of monochlorobenzene, and 1- (1-n-butoxy-2-propoxy) -2-
A mixture of 743.3 g (3.91 mol) of propanol and 324.0 g (4.10 mol) of pyridine was added dropwise at 4 to 4 hours at an internal temperature of 2 to 10 ° C. while stirring under ice cooling.
Aged at 25 ° C. for 5 hours. The obtained reaction solution is filtered,
The filter cake was washed with 800 ml of monochlorobenzene. The mixed solution of the filtrate and the washing solution was desolvated under reduced pressure to obtain a crude mono (1- (1
1,226 g of -n-butoxy-2-propoxy) -2-propyl) phosphoric dichloride were obtained. Next, while performing nitrogen bubbling on a 3 l reaction flask charged with 900 g of water, the obtained crude mono (1- (1-n-butoxy-2-) was obtained.
Propoxy) -2-propyl) phosphoric dichloride 122
6 g was dropped at an internal temperature of 50 to 60 ° C. over 3.5 hours.
Aged at 0 ° C. for 3 hours (PH = 1 or less). After continuing nitrogen bubbling until the temperature was cooled to room temperature, 1800 ml of monochlorobenzene and 140 g of rock salt were added thereto to carry out extraction and separation. The lower organic layer was washed with 400 ml of 5% hydrochloric acid and then with 400 ml of water. Next, 30 g of activated carbon (Shirasagi C) was added to the lower organic layer, and the mixture was stirred at room temperature for 1 hour and filtered. The obtained filtrate was further added to 400 ml of water.
, And the solvent was removed under reduced pressure. Finally, the residue was filtered (3 μm) at room temperature to give 889.2 g
(Crude yield 84%) of mono (1- (1-n-butoxy-2)
-Propoxy) -2-propyl) phosphoric acid was obtained. The composition of the obtained phosphoric ester was as follows.

[Table 1] The identification data obtained by purification by silica gel column chromatography is described below. <MS spectrum (FAB (Pos.))> M / z = 271 (M + H) + < ¹ H-NMR> → see FIG. 1 < ¹³ C-NMR> → see FIG. 2

Example 2 (Synthesis of Phosphate Ester-2) 383.3 g of phosphorus oxychloride (2.
50 mol) and 1800 ml of toluene.
-N-butoxy-2-propoxy) -2-propanol 951.4 g (5.00 mol) and pyridine 553.7 g
(7.00 mol) was added dropwise over 2.5 hours at an internal temperature of 25 to 30 ° C. while stirring under ice cooling.
Aged at 0 ° C. for 22 hours. The obtained reaction solution is filtered,
The filter cake was washed with 500 ml of toluene. The mixed solution of the filtrate and the washing solution was desolvated under reduced pressure to obtain 1142.2 g of crude di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid chloride. Next, while performing nitrogen bubbling on a 3 liter reaction flask charged with 1000 ml of water,
The obtained crude di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid chloride was treated at an internal temperature of 50 to 60.
The mixture was added dropwise at 0.5 ° C. over 0.5 hours, and aged at 60 ° C. for 5 hours. After continuing nitrogen bubbling until it was cooled to room temperature, 1000 ml of toluene was added thereto to carry out extraction and separation. The upper organic layer was washed with 500 ml of 5% hydrochloric acid and then with 500 ml of water. Next, 30 g of activated carbon (Shirasagi C) was added to the upper organic layer, and the mixture was stirred at room temperature for 1 hour and filtered. The obtained filtrate was further washed twice with 500 ml of water and subjected to desolvation topping under reduced pressure. Finally, the residue was filtered (3 μm) at room temperature to obtain 1022.3 g (92% crude yield) of di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid. The composition of the obtained phosphoric ester was as follows.

[Table 2] The identification data obtained by purification by silica gel column chromatography is described below. <MS spectrum (FAB (Pos.))> M / z = 443 (M + H) + < ¹ H-NMR> → see FIG. 3 < ¹³ C-NMR> → see FIG.

Example 3 (Synthesis of phosphoric ester-3) 76.6 g of phosphorus oxychloride was placed in a 500 ml reaction flask.
(0.50 mol) and 200 ml of butyl acetate,
-(1- (1-n-butoxy-2-propoxy) -2-
124.2 g (0.5) of propoxy) -2-propanol
0 mol) and 50.6 g (0.50 mol) of triethylamine while stirring under ice-cooling at an internal temperature of 15 to 2 g.
The mixture was added dropwise at 0 ° C over 0.5 hours, and aged at 25 ° C for 3 hours. The obtained reaction solution was filtered, and the filter cake was washed with 10% butyl acetate.
Washed with 0 ml. The mixture of the filtrate and the washing was desolvated under reduced pressure to obtain crude mono (1- (1- (1-n-butoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid dichloride. Next, 1 was charged with 200 ml of water.
While performing bubbling of nitrogen through the reaction flask, the obtained crude mono (1- (1- (1-n-butoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid dichloride was added at an internal temperature of 50 to 60. At 0.5 ° C over 0.5 hours,
Aged at 60 ° C. for 5 hours. After continuing nitrogen bubbling until it was cooled to room temperature, 300 ml of butyl acetate was added thereto to carry out extraction and separation. The upper organic layer is made of 5% hydrochloric acid water 200 m
1 and then with 200 ml of water. Next, 5 g of activated carbon (Shirasagi C) was added to the upper organic layer, and the mixture was added at room temperature for 1 hour.
After stirring for an hour, the mixture was filtered. The obtained filtrate is further added to water 20
After washing twice with 0 ml of water, desolvation topping was performed under reduced pressure. Finally, the residue was filtered (3 μm) at room temperature to give
6.0 g (crude yield 95%) of mono (1- (1- (1-n
-Butoxy-2-propoxy) -2-propoxy) -2
-Propyl) phosphoric acid was obtained. The composition of the obtained phosphoric ester was as follows.

[Table 3] The identification data obtained by purification by silica gel column chromatography is described below. <MS spectrum (FAB (Pos.))> M / z = 329 (M + H) + < ¹ H-NMR> → see FIG. 5 < ¹³ C-NMR> → see FIG.

Example 4 (Synthesis of phosphoric acid ester-4) 411.6 g of phosphorus oxychloride (2.
68 mol) and 1500 ml of monochlorobenzene, and 1- (1- (1-n-butoxy-2-propoxy)
-2-propoxy) -2-propanol 1000.0 g
(4.03 mol) and a mixed solution of 424.6 g (5.37 mol) of pyridine were stirred under ice-water cooling while the internal temperature was 25 to 25 mol / min.
The solution was added dropwise at 30 ° C over 3 hours, and aged at 30 to 40 ° C for 15 hours. The obtained reaction solution was filtered, and the filter cake was washed with 500 ml of monochlorobenzene. The mixture of the filtrate and the washing solution was desolvated under reduced pressure, and mono (1- (1- (1-n-butoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid dichloride and di (1 -(1- (1-n-
Butoxy-2-propoxy) -2-propoxy) -2-
A mixed solution of propyl) phosphoric acid chloride was obtained. Next, water 1
While performing nitrogen bubbling on a 3 l reaction flask charged with 000 ml, the obtained mono (1- (1- (1-n
-Butoxy-2-propoxy) -2-propoxy) -2
-Propyl) phosphoric acid dichloride and di (1- (1- (1
-N-butoxy-2-propoxy) -2-propoxy)
-2-propyl) phosphoric acid chloride mixture at an internal temperature of 50 to
The solution was added dropwise at 60 ° C. over 1 hour and aged at 60 ° C. for 5 hours. After completion of the reaction, nitrogen bubbling was continued until the mixture was cooled to room temperature, and then 1000 ml of monochlorobenzene was added to carry out extraction and separation. The obtained organic layer was washed with a 5% aqueous hydrochloric acid solution (50%).
It was washed with 0 ml and then with 500 ml of water. Next, 30 g of activated carbon (Shirasagi C) was added to the organic layer, and the mixture was stirred at room temperature for 1 hour and filtered. The obtained filtrate is further added to water 5
After washing twice with 00 ml, desolvation topping was performed under reduced pressure. Finally, the residue was filtered (3 μm) at room temperature and 10
54.9 g (crude yield 94%) of mono (1- (1- (1-
n-butoxy-2-propoxy) -2-propoxy)-
A mixed solution of 2-propyl) phosphoric acid and di (1- (1- (1-n-butoxy-2-propoxy) -2-propoxy) -2-propyl) phosphoric acid was obtained. The composition of the obtained phosphoric ester was as follows.

[Table 4]

Example 5 (Preparation of Phosphoric Ester) The mono (1- (1-n-butoxy-2) obtained in Example 1 was obtained.
(Propoxy) -2-propyl) phosphoric acid (400 g) and di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid obtained in Example 2 (600 g) were mixed to obtain a monoester and a diester. 1000 mixed phosphate esters
g was adjusted. The composition of the obtained mixed phosphate was as follows.

[Table 5]

Example 6 (Synthesis of phosphoric acid ester-5) Phosphorus oxychloride 137.1 was placed in a 1000 ml reaction flask.
g (0.89 mol) and 500 ml of monochlorobenzene were charged, and 1- (1- (1-methoxy-2-propoxy)) was added.
-3-propoxy) -2-propanol 368.8 g
(1.79 mol) and a mixture of pyridine (169.7 g, 2.15 mol) and an inner temperature of 0 to 2 while stirring under ice-water cooling.
The solution was dropped at 5 ° C over 2 hours, and aged at 25 to 30 ° C for 8 hours. The obtained reaction solution was filtered, and the filter cake was washed with 800 ml of monochlorobenzene. The mixed solution of the filtrate and the washing solution was desolvated under reduced pressure, and crude di (1- (1- (1-methoxy-2)
550.0 g of -propoxy) -2-propoxy) -2-propyl) phosphoric acid chloride were obtained. Next, 500 ml of water
While performing nitrogen bubbling on the 2 l reaction flask charged with, the crude di (1- (1- (1-methoxy-2) -2
-Propoxy) -2-propoxy) -2-propyl) phosphoric acid chloride was added dropwise at an internal temperature of 50 to 55 ° C over 1 hour, and the mixture was aged at 60 ° C for 5 hours. After completion of the reaction, nitrogen bubbling was continued until the mixture was cooled to room temperature, and then 500 ml of monochlorobenzene was added to carry out extraction and separation. This extraction operation was performed again. The obtained organic layer was washed with 200 ml of 5% hydrochloric acid and then with 200 ml of water. Next, 10 g of activated carbon (Shirasagi C) was added to the organic layer,
After stirring at room temperature for 1 hour, the mixture was filtered. The obtained filtrate was further washed twice with 200 ml of water and subjected to desolvation topping under reduced pressure. Finally, the residue was filtered (3 μm) at room temperature to give 318.4 g (75% crude yield) of di (1- (1-
(1-methoxy-2-propoxy) -2-propoxy)
(-2-propyl) phosphoric acid was obtained. The composition of the obtained phosphoric ester was as follows.

[Table 6] The identification data obtained by purification by silica gel column chromatography is described below. <MS spectrum (FAB (Pos.))> M / z = 475 (M + H) + < ¹ H-NMR> → see FIG. 7 < ¹³ C-NMR> → see FIG. 8

Example 7 364 g (1.93 mol) of m-xylylene diisocyanate and 0.070 g (100 pp) of dibutyltin dichloride were used.
0.70 g of the phosphoric ester of Example 5 in the mixture of m)
(1000 ppm) and mixed and dissolved under nitrogen. Next, 336 g (1.29 mol) of 1,2-bis (2-mercaptoethylthio) -3-propanethiol was added to this solution.
Was added and mixed, and mixed and defoamed under reduced pressure. After defoaming, inject into the prepared mold beforehand,
The temperature was gradually increased from room temperature to 120 ° C., and the composition was cured by heating for 20 hours. After cooling, the lens obtained by releasing the mold was colorless and transparent, and had a refractive index Nd of 1.660 and an Abbe number νd of 32. Table 7 shows the evaluation results of the release agents.

Examples 8 to 12 and Comparative Examples 1 to 7 The same tests as in Example 6 were carried out by changing the amount and type of the release agent. Table 7 shows the results.

[0057]

[Table 7]

(Structure of Zelek UN) (Structure and composition of JP-506H) (Structure of Plysurf A212E)

Example 13 Bis (isocyanatomethyl) norbornane 348 g
(1.69 mol) and 0.28 g of dibutyltin dichloride
(400 ppm) was mixed with 0.7 g (1000 ppm) of the phosphoric acid ester of Example 4 under nitrogen. Next, 171 g of pentaerythritol tetrakis (3-mercaptopropionate) (0.3 g) was added to the solution.
5 mol) and 4,8-bis (mercaptomethyl) -3,
6,9-trithia-1,11-undecanedithiol 1
81 g (0.49 mol) was added and mixed, and mixed and defoamed under reduced pressure. After the defoaming was completed, the mixture was poured into a molding mold prepared in advance, gradually heated from room temperature to 130 ° C., and cured by heating for 20 hours. After cooling, the lens obtained by releasing the mold is colorless and transparent, and has a refractive index Nd of 1.59.
4, Abbe number νd = 43. Table 8 shows the evaluation results of the release agents.

Examples 14 to 17 The same tests as in Example 13 were carried out, except that the type and amount of the release agent were changed. Table 8 shows the results.

[0061]

[Table 8]

Example 19 425 g of bis (isocyanatomethylthio) methane (2.
23 mol) and 0.035 g of dibutyltin dichloride (50
ppm) of the phosphoric acid ester of Example 5
g (1000 ppm) and mixed and dissolved under nitrogen. Next, 2,4-bis (mercaptomethyl) -3 was added to this solution.
275 g of thia-1,5-pentanedithiol (1.1
2 mol) were added and mixed, and mixed and defoamed under reduced pressure.
After the defoaming was completed, the mixture was poured into a molding mold prepared in advance, gradually heated from room temperature to 120 ° C., and cured by heating for 20 hours. After cooling, the lens obtained by releasing the mold is colorless and transparent, has a refractive index Nd of 1.694, and an Abbe number νd.
= 33. There were no problems with the degree of coloring, transparency, and releasability.

[0063]

According to the present invention, a transparent resin is easily released from a molding die, and a product having extremely high transparency can be obtained.

[Brief description of the drawings]

FIG. 1. ¹ H-NMR of mono (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid

FIG. 2: ¹³ C-NMR of mono (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid

FIG. 3 ¹ H-NMR of di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid

FIG. 4: ¹³ C-NMR of di (1- (1-n-butoxy-2-propoxy) -2-propyl) phosphoric acid

FIG. 5 ¹ H-NMR of mono (1- (1-n-butoxy-2-propoxy) -2-propoxy) phosphoric acid

FIG. 6: ¹³ C-NMR of mono (1- (1-n-butoxy-2-propoxy) -2-propoxy) phosphoric acid

FIG. 7: Di (1- (1-methoxy-2-propoxy)-
¹ H-NMR of 2-propoxy) propyl) phosphoric acid

FIG. 8: Di (1- (1-methoxy-2-propoxy)-
¹³ C-NMR of 2-propoxy) propyl) phosphoric acid

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F202 AA42 AB07 AH73 AH74 CA01 CA11 CM55 4H050 AA01 AA02 AA03 AB99 WA15 WA23

Claims (6)

[Claims] [Claim 1] The following formula (1) (In the formula, m represents 1 or 2, n represents an integer of 2 to 3, R ₁ represents a residue having 1 to 20 carbon atoms excluding a phenyl group, and R ₂ and R ₃ each represent a hydrogen atom , A methyl group and an ethyl group, provided that R ₂ and R ₃ are not both hydrogen atoms). 2. The following formula (2): (In the formula, m represents 1 or 2, n represents an integer of 2 to 3, R ₁ represents a residue having 1 to 20 carbon atoms excluding a phenyl group, and R ₂ and R ₃ each represent a hydrogen atom , A methyl group and an ethyl group, except that both R ₂ and R ₃ are hydrogen atoms, and X represents a halogen atom.) The method for producing a phosphate according to claim 1. 3. A release agent containing the phosphoric ester according to claim 1. 4. A transparent resin containing the release agent according to claim 3. 5. The transparent resin is a transparent optical material.
The transparent resin described. 6. The transparent resin according to claim 4, wherein the transparent resin is a plastic lens.