JPS5821687A - (meth)acryloyloxyalkyl dihydrogenphosphate and its preparation - Google Patents

Abstract

NEW MATERIAL:A compound of formulaI(n is an interger 5-12; R is H or methyl). EXAMPLE:5-(Meth)acryloyloxypentyl dihydrogenphosphate. USE:A dental adhesive, capable of exhibiting improved water-resistant adhesive force to a metal and the tooth, and widely usable as adhesive monomers in structural adhesives, coating materials for a metal, metallic surface treating agents, etc. PROCESS:An alkylene diol of formula II is esterified with (meth)acrylic acid to give a diol mono(meth)acrylate, which is then reacted with phosphorus oxychloride. The P-Cl bond in the resultant compound is then hydrolyzed to afford the compound of formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound (meth)acryloyloxyalkyl dihydrodiene phosphate and a method for producing the same.

The above compound has the general formula (where n is an integer from 5 to 12, B is H or CH
represents. ) It is a (meth)acrylic acid ester monomer having a phosphoric residue [-PO(OH)2] and a radically polymerizable double bond. Such compounds exhibit excellent water-resistant adhesion to metals and teeth.

In the general formula (A), m is 2 and B is CH, 2-methacryloyloxyethyl dihydrogen phosphate is easily synthesized by reacting 2-hydroxyethyl methacrylate with phosphorus pentoxide or phosphorus oxychloride,
It is a well-known fact that monomer compositions containing this compound adhere well to metals such as aluminum iron, antimony, etc. (eg, JP-A No. 100120/1983). Although the above-mentioned JP-A shows a general formula that includes compounds up to ■ = 6, what is specifically shown is a compound where n = 2, and when n is 3 or more, it has not been actually synthesized. ,
There is no record indicating that it was used. The present inventors discovered a surprising fact in the process of conducting a detailed study on the adhesive strength of (meth)acrylic ester monomers having phosphoric residues to metals and tooth substance for the purpose of developing dental adhesives. ．． That is, the above-mentioned 2-methacryloyl dihydrogen phosphate was added to O. The adhesion strength and water resistance of the adhesive composition containing 5 to 5% by weight to Ni-Cr alloy and stainless steel are disclosed in JP-A-54-12338.
4- exhibiting adhesive action on metal and tooth substance disclosed in No.
In addition to being significantly inferior to that of methacryloxyethyl trimellitic acid, it showed no adhesive effect on teeth at all. On the other hand, compounds of general formula (A) with m of 5 to -12 adhered extremely strongly to metals and teeth, and had water resistance several steps higher than that of 4-methacryloxyethyl trimellitic acid. As described above, there is an essential difference in the adhesion to metals and teeth between the compound of general formula (4) where m is 2 and the compound where m is 5 to 12.

Although the compound of n = 2 has been described as an adhesive monomer for metals in numerous documents including the above-mentioned JP-A,
It is presumed that the reason why no compounds with n=5 to 12 that were significantly superior to these were found was that these compounds were not available as industrial raw materials or reagents. 2-
While (meth)acryloyloxyethyl dihydrodiene phosphate is easily synthesized industrially, the compound of the present invention uses (meth)acrylic acid monoester of alkylene wall, which is an intermediate raw material for synthesis, as a single component. There is a disadvantage that it cannot be obtained. If you try to synthesize this compound using current technology, you will inevitably end up with a monoester. This results in a mixed system consisting of diester and its raw material components. Because this compound is polymerizable and has a high boiling point, it is extremely difficult to distill it, and separation by chromatography is the only option, but the monoester separated by this method is extremely expensive, so (n = 5 to 12, R = B, CH.)
There has been no attempt at synthesis using this as a raw material. Therefore, the present inventors used the monoester in the state of a mixture of monoester and diester without isolating it from the mixed system, and n
We have devised a method to easily attack the compound of general formula (A) where = 5 to 12, and the resulting compound adheres strongly to metals and tooth structure, something that could never be achieved with known adhesives. I discovered that.

That is, the present invention is a (meth)acryloyloxyderkyl di^ide diene sulfate represented by the above general formula. A specific example is &0 compound. S-(meth)acryloyloxydecyl di^hydrodiene), 4-(meth)acryloyloxyhexydrodiene phosphate, 7-(meth)acryloyloxydecyl di-11-hydrodiene), 11-( Meta) aqayloxyoctyl dihydrogene sulfate.

! -(meth)acryloyloxynonyl di, r''% idlodiene phosphate, 10-(meth)acryloyloxydecyl diI)ydrodiene phos7a),
11-(Meth)acryloyloxyundecyl dihydrogene umbrella sulfate.

*X-(Me#) Acryloyl oxide doderyl dihydroliene phosphate.

These compounds are as follows! Manufactured by a step process. In the first step, esterification reaction between (meth)acrylic acid and alkylene diol is performed to synthesize raw materials to diol mono(meth)acrylate. Specifically, it is desirable to conduct the treatment under the following conditions, per mole of diol.

0.5 mol to 1.5 mol of (meth)acrylic acid is charged, and an esterification reaction is carried out without a solvent in the presence of an acid catalyst at 120° C. or below in an I<buty method. The amount of (meth)acrylic Shun O used per 1 liter of diol is 0. less than s mol or 1.5
If it exceeds the molar amount, the yield of monoester will decrease significantly, which is not preferable.As an esterification catalyst, use a strong acid such as sulfuric acid or sulfuric acid in an amount of 0.1 to 10% by weight based on the total amount charged.
Add. In addition, hydroquinone monomethyl ether, hydroquinone, 2
．． Polymerization inhibitors such as 2'-methylenebis(4-ethyl-6-4art-butylphenol) and 2.2'-methylenebis-6--butyl-p-cresol (meth)
Add 100 to 10,000 ppm based on acrylic acid.

Further, air or oxygen is blown into the reaction solution to prevent polymerization, but if the degree of one reaction exceeds 120C, there is still a risk of polymerization. Therefore, 1 bar below 120℃ is 100C
It is preferable to carry out the reaction while distilling the produced water under reduced pressure. When no water is distilled out, the reaction is stopped, and the reaction solution is washed with an alkali priming layer solution to remove unreacted (meth)acrylic acid. Next, unreacted diols are removed. For water-soluble diols having 7 or fewer carbon atoms, the above reaction solution is washed with water nine times to reduce the diol to a level that does not support the next O reaction. The amount can be reduced. On the other hand, the number of carbon
It is extremely difficult to remove the above water-refractory diols by washing with water, but the reaction solution after washing with alkaline is treated with a vp polar organic stimulant such as n-hexane, cyclohexane, benzene, toluene, etc. It can be removed by diluting it 2 to 10 times and adjusting the pH of the precipitated diol.

The mixture of monoester and diester thus obtained is used as a raw material for the next phosphoric acid esterification reaction after determining the mixing ratio by an analytical means such as high-performance liquid chromatography (hereinafter abbreviated as HLO).

The second step is a phosphoric acid esterification reaction, in which phosphorus oxychloride is converted into ethyl ether, tetrahydro7rane, 1.4-
Dioxane, ethyl acetate, dichloromethane, lyaloform, 1,2-lichloromethane, benzene, etc. at a concentration of 5%
Dilute it to a level that does not exceed the following and place it in a reaction vessel.
Cool to -6 ot. The amount of phosphorus oxychloride used is 1.0 to 2.0 moles per mole of hydroxyl group of the monoester.

Polymerize the previously synthesized diol monoester, diester island compound, and the monoester with equimolar or slightly less 1110 tertiary amines (e.g., triethylamine, tributylamine, pyridine, N-methyl phosphorus, etc.). The reaction solution is added dropwise to the cooled reaction chamber either as it is or after diluting it with a solvent such as ethyl ether.The reaction solution is vigorously stirred at the time of addition, and the reaction temperature is maintained between 0°C and -60°C.
If the temperature exceeds 0C, the phosphoric acid diester, which is a by-product, will easily be produced, and if the temperature is below -60C, the reaction rate will slow down.
Continue stirring the reaction solution at ~-40CO, and the @a
Raise the reaction temperature to ℃, dropwise add water and 5th class atom, and unreacted □? Hydrolyze the -07 bond. At this time, water is added in a molar amount in excess of the estimated residual P-01 bond, and the tertiary amine is added dropwise so that the total amount of the tertiary amine is three times that of phosphorus oxychloride.

After completion of dripping, the hydrolysis of Day CI is completed at O℃~Tofutsu.
The reaction is continued until the precipitated ammonium salt is filtered out. The P solution is concentrated by removing the organic solvent. The desired synthetic compound has the general formula (a) and a noble number -s
-8, the concentrated solution is extracted with an aqueous solution of sodium bicarbonate, sodium carbonate, potassium bicarbonate, or potassium carbonate, and the resulting solution is further extracted with ether to remove the di(meth)acrylate and the main An aqueous solution of the sodium or potassium salt of the product phosphoric acid ester and the by-product phosphorus ester is obtained.

Next, lI [phosphoric acid diester salt is extracted and removed from the aqueous solution with chloroform. The aqueous solution is made acidic with phosphoric acid, hydrochloric acid, sulfuric acid, etc., and the phase-separated phosphoric acid sonoester is extracted with an organic laxative such as ethylnityl, ethyl acetate, or benzene. After adding a desiccant to the carcass extract and dehydrating it, 100 to 3000 ppm of a polymerization inhibitor or antioxidant, such as 2,6-di-1-butyl-P-cresol, is added, and the solvent is removed under reduced pressure, thus leaving phosphorus as a residue. An acid sonoester is obtained. On the other hand, when the number of carbon atoms is n=9-12, the concentrated solution is extracted with a saturated hydrocarbon solvent such as n-hexane, cyclohexane, etc. to remove diol O di(meth)acrylate and phosphoric diester. Add a polymerization inhibitor or antioxidant to the phosphoric acid monoester concentrate thus purified.
ppm to 5,000 ppm and the residual solvent is removed under reduced pressure to obtain a phosphoric acid monoester of liquid.

The structure of the OQ acid ester compound of the present invention is confirmed by NMIL
It is also possible to conduct tests based on elemental analysis.

In the case of 10g6 (3DOJs #1 solution measured by NMR), in the case of 17cripyl oxyrealkyl dihydrodiene phosphate, there was a signal of 2m ethylenic protons at I depths 5.5 and 6.1, and #gj? Signal of methyl proton, #ff15.7-4.Signal of methylene proton adjacent to oxygen atom, #==1.5-1.9
Signal of methylene proton in Niso ol+.

A proton signal of a phosphate group is observed near ays~12. On the other hand, in acryloyloxyalkyl dihydrogene sulfate, 'a=s, y.

(1, (sl (5 types of ethylenic proton signals h,
Signals of methylene protons adjacent to oxygen are observed at ays, y~4.3; signals of other methylene protons are observed at aml, s~1.9, and signals of phosphate group protons are observed near Jg8-12. The purity of the compound is determined by column K.
It can be charged at HL (3) using Unisil Q C+a (Gas Kuro Kogyo).

Various metals (Fe, Ni, Or, C
U, Zn, etc.) and dental calligraphy alone or in combination with other ethylenically unsaturated compounds, and radical polymerization is performed.
Dental adhesives (adhesives applied to teeth during tooth restoration) exhibit high adhesive strength with excellent water resistance when polymerized and cured using means such as initiators, heat, and light.

Adhesives for bonding inlays, crowns, etc. to teeth, dentition pressure adhesives, adhesives for holding bridges, casts, etc., dental composite filling materials, etc.), structural adhesives, paints for metals, metals It is used in a wide range of applications as an adhesive monomer such as surface treatment agents.

In particular, when the compound of the present invention is used in a dental adhesive,
(a) Cough suppressants as adhesive monomers (compounds with 1≧8 or more are particularly preferred in terms of adhesiveness to teeth).
It is preferable to use a composition consisting of a copolymerizable vinylated metal material and a curing agent.The content of the adhesive compound in the composition is preferably 0.5 to the total monomer from the viewpoint of adhesive properties. % by weight or more, usually 1.5-SO weight*
Used in c+sis. As copolymerizable vinyl compounds, those conventionally used in dental adhesives can be used, including ants, styrene, vinyl acetate, and (meth)acrylate monomers [methyl (meth)acrylate.

2-hydroxyethyl (meth)acrylate, tetraethylene glycol di(meth)acrylate.

Neopentyl glycol di(meth)acrylate.

Bus-GMA, methylolpropanetri(meth)
Acrylate, bisphenol-mushi (meth)acrylate, etc., JP 1852-11308? [Refer to the description in the issue]. These are appropriately selected to adjust the viscosity, wetting characteristics, curing characteristics, mechanical properties, etc. of the adhesive.

As hardening agents, benzoyl peroxide, azobisisobutyronitrile, and tributylborane are used in the dental field.

Aromatic sulfinic acids (or salts), aromatic sulfinate/diacyl peroxide/aromatic tertiary acylbases, etc. are used. A photosensitizer (such as benzoin methyl ether) is also used. For hardening agents, see JP-A-55
-110637, 54-111 jf No. O position is referred to. Furthermore, a volatile organic solvent (such as ethanol), an inorganic filler such as crystallite d, and an organic filler such as polymethyl methacrylate powder may be added to the above composition.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 Methacrylic acid 140f (1,4 mol), 1,4-hexanediol 19Oj (1f mol), p-)luenesulfonic acid 157,2,2'-methylenebis(4-ethyl-4
-tert-butylphenol) q, 4f 5 Q O
Place in a cc three-neck flask and heat under reduced pressure (100-15・■
Hf) The reaction was continued for several hours while heating to 90° C. and blowing oxygen until water stopped distilling out.

When distillation stopped, the reaction solution was cooled to room temperature, transferred to a separating funnel, and washed with 5% sodium carbonate water until the washing water showed alkalinity. Furthermore, the reaction solution was washed five times with 500 g of water. After dehydration with anhydrous sodium sulfate, hehydroquinone and methyl ether (hereinafter referred to as MEHQ) were added to the reaction solution.
(abbreviated as ) was added to the solution by sowing, heated to 80° C., and residual water was distilled off. '1? Monoesters and diesters of IIp0
An al1 compound was obtained.

As a result of analyzing the metal sample by HLC, the monoester content was 75 mol%, and the residual amount of diol O was 0.5% by weight or less.

100 c of Qn oxychloride 559 (0,746 mol)
The mixture was poured into a 1fD reaction volume in cO methyl ether and cooled to -40C. Previously synthesized methacrylic acid ester mixture ILf (containing 0.5 mol of monoester)
and triethylamine 519 (0.54 mol) were dissolved in 10 floc of ethyl ether, placed in a 300 cc dropping funnel, and connected to a reaction vessel. Stir the phosphorus oxychloride solution vigorously and dry N! While blowing gas, the solution was slowly added dropwise. After the completion of the dropwise addition, the reaction solution was kept at 10°C for 5 hours, and then water Hop, which had been heated to 0°C, was added to the dropping funnel while continuing to stir. dripped. Subsequently, triethyl ane 72,9f (072 mol) was added to 10@Ce
After dropping 6 drops of *S into ethyl ether, 10
The reaction solution was kept at 0° C. and stirring was continued. Thereafter, the precipitated triethyluene O hydrochloride was separated using a glass filter, and 40° C. was added with FI [lCMIHQ 104]. fk! -f was distilled off under reduced pressure to obtain a nonvolatile liquid residue. Disperse the liquid in 2 ml of water and add 6sy (o, 6mol) of sodium carbonate while stirring vigorously under water cooling.
was added little by little to neutralize it. When the foaming subsided, the dispersion was transferred to a separating funnel and diluted with 100 cc of ethyl ether.
It was extracted and washed four times with 100 cc of chloroform. Next, 6t4NHCl was added to the #1 water wave under ice cooling to make it acidic, and the phase-separated oily substance was extracted three times with ethyl ether. After combining each extract and drying with anhydrous sodium sulfate, add 10WIg of MEHQ,
A colorless transparent liquid of 67f was obtained by mixing W.

Use 10% 0DOj of skeletal liquid as g liquid at room temperature! OMH
When we performed the measurement of MR6,05 and 5
．． 5 is an ethylenic proton signal, J = j, 9 is a methyl proton signal, a = S, S ~ 4.2 and 1.2 ~ 1.8 are hexamethylene residue proton multiple signals, Jxlj An acidic proton O signal of phosphoric acid was observed nearby. In addition, the result of elemental analysis is 0:44.5
%, H near, 8%, 0:56.5%, P:11.2% (
Calculated value C: 45.1%, H near, 2%, 0!36.1%
, P: 11.6%), it was confirmed that the compound was methacryloyloxyhexyl dihydrodiene phosphate. HLC (Column: Unisil Q C+
As a result of analysis with ), the purity is! It was found to be 7-9%.

Example 2 An experiment was conducted under exactly the same conditions as in Example 1, except that 170f (1.6 mol) of 1.5-bentanediol was used in place of hexanediol, and diol sonoester, A diester bulk product was obtained. After determining the monoester content by HLC, the monoester 0. A phosphoric acid esterification reaction was carried out using an amount o1[11/41e corresponding to S mole], and then 11 was carried out for 1 minute in exactly the same manner as in Example 1 to obtain 6110 acidic nonvolatile liquid. NMIL measurement 1 of the compound Measurement 1 Element Ct 42.4% (42
，? ), H near, 1% (4,8), 0:38.5% (A
s, 1), ? : 11.8% (12j), but 0
The value in the box is a calculated value, and it was confirmed that it was methacryloyloxypentyl dihydrodiene phosphate. HLC analysis result is 94~! It was 8%.

Example S Acqq acid 14@l (1,9% k), 1, 4
-hexanediol 1?0j (lj mol), P-) luenesulfonic acid 15f, 2,2'-methylenebis(4-diol?4-t@rt-buty47!/-4)Oj f
was placed in a 500 oc flask, and while oxygen was blown through the capillary, the produced water was distilled out under conditions of 80° C. and a reduced pressure of 100 to 200 μHfO. After the reaction was stopped in the same manner as in Example 1, washing with alkaline water, washing with water, and dehydration were performed to finally obtain acrylic acid monoester and diester mixture 175f. The monoester content of the mixture was determined by HLO to be 68 mol%. Next, the mixture 51B, 6
Phosphorus oxychloride 5if is obtained using the same method as in Example 1.
(0.34 mol) and isolation of the η-acid monoester, a colorless, clear, non-pruritic liquid of 42IO was obtained. The compound was analyzed by NM elemental analysis (0:42.7% (
42,9), II wealth 7,1% (4,8) @0sBI1.
1% (Ill, 1), Pll, 94 (12, is),
Based on the results in ), it was confirmed that it was acryloyloxyhexyl dihydrogen sulfate. HLO or 4 purity! S~? Example 4 In the run ms, 1.6-hexanediol was found to be 1.5%.
An experiment was conducted under exactly the same conditions as in Example 3, except that -bentanediol 110f (1.6 mol) was used, and a mixture of diol monoester and diester was obtained. After determining the monoester content by HLO, a phosphoric esterification reaction was carried out using the mixture in an amount corresponding to 0.3 mol of the monoester.

Separation and purification were performed in exactly the same manner as in Example 1, and 48f
An acidic non-volatile liquid was obtained. NMR analysis and elemental analysis of the compound (c: 4a, s% (40j), 1156.5% (
4,4), 0:4G. 0% (40j), P:1! S, 0
%(13,O).

The values in () are calculated values, and it was confirmed that the product was 1% acryloyloxypentyl dihydrogen phosphate. The purity of HLO analysis is 9s~!
It was 7g6.

Example 5 Mell phosphoric acid 140f (lj mol), t, 10-f
Put candiol 230f (lj solu), p-toluenesulfanoic acid 1'4f, 2,2'-methylenebis(4-ethyl ichiban-1,11-butylphenol) fi, and AI into a 5eacH flask, and add 80 It was heated to a temperature of 0.degree. C. to obtain a uniform #1 temperature. 100-150-Hp inside the flask
Reduce the pressure to 100%, blow in oxygen, and stir! The esterification reaction was carried out using OC, and the produced water was distilled off. When no water distills out, stop the reaction, cool it at room temperature and add 500 cc of the same hexane to dilute it.
In step III, when the cleaning solution was alkaline, rum was added and the solution was left refrigerated at 5°C. One day later, the precipitated unreacted diol was separated again by P, MICHQ 40 was added to the r liquid, 1-hexane was removed under reduced pressure at 80°C or less, and ib a
9-ol monoester of “”y.

A diester mixture was obtained. Analysis of the mixture by HLC revealed that the monoester content was 45wm67%, and only traces of unreacted diol were contained.

100 c of phosphorus oxychloride 551 (0,!14 mol)
11111 to cOz chill ether and spring l11168!
The mixture was placed in a Ohshun oven and cooled at -401:l. The monoester 4r product 12sy (monoester 0.
5 mol) and triethylane 37 f (0,54
mol) in 120 cc of ethyl ether,! 1oo
It was placed in a cc dropping funnel and connected to 1 reaction volume. The phosphorus oxychloride solution was vigorously stirred, and nine drops of the above-mentioned solution 0III were slowly added while blowing dry nitrogen and gas. 3 hours after completion of dripping! The 5OCK reaction solution was kept and then heated to e°C.

Next is water! The mixture was placed in a 10 ff dropping funnel and added dropwise while stirring. Furthermore, triethylamine 72.9f (0,1
'1 mole) was dissolved in 100 cc of ethyl ether and added dropwise. After the completion of the dropwise addition, the reaction solution was diluted with acFcd for 10 hours.
and continued stirring slowly. After that, the precipitated triethylamine hydrochloride was filtered through a glass filter.
After repeatedly washing the F solution with water, dehydrating and drying it, MIHQ20q
was added, and ethyl ether was distilled off under reduced pressure at 40°C to obtain a liquid residue. Wash the liquid repeatedly with n-hexane,
Diesters of diols, diesters of phosphoric acid, Im Ex. 11
Then, the chitin dissolved in the phosphoric acid monoester lI was distilled off under reduced pressure to obtain a liquid compound 73f.

Regarding the 10% CDCjls@ solution of the metal compound, 10 Mu
Tomi NMR@Sada was performed at Tomi ■. As a result, #m41!1
and ethylenic proton O signal at 5.5, 4M1.
Add methyl group proton signal to 9, 1wxs, 8 to 4
．． 2 and 1.2 to 1.8 have multiple signals of decamethylene residue protons, and the acid proton value of phosphoric acid is around Jw9.7: O: 52.2%, H: s, 4.0: 29.
1! , P: t, 6), it was confirmed that the compound was methacryloyloxydecyl dihydrogene sulfate.

HLO (force xy A: Unisil QO1@)
Conclusion* analyzed.

The purity was 92-95%.

Example 6 In Example 5, 1.10-decanediol was added to 1°1!
-Fftj'n0 all 2! (Other than replacing If (1, Jimoj), an experiment was conducted under exactly the same conditions as in Example 5 to obtain a diol monoester and diester mixture,
After determining the monoester content by HLO, the mixture in an amount corresponding to 0.3 mol of sonoester was used to carry out the q-acid esterification reaction. A liquid compound of 75f was obtained. NMIL measurement of the metal compound 9 Measurement 9 Element 0:S5. s% (54,
? ),■:? j%(1,9), O:! 7,0% (27
,4), Ps 8.5% (8,8), Values in parentheses are calculated values. ], we confirmed that methacryloyl oxide dodecyl dihydrodiene phosphate was a compound. As a result of HLO analysis, the purity was 92-95%.

Example 7 Aku Qk acid 11Sf (1,4 mo4), 1, 10
-Decanediol 2NOf (1,S mol), P-toluenesulfanoic acid 1if, 2,2'-methylenebis(4-ethy4-4-t@rt-butykl)-4) 0.61 to 500 Place it in a 100-million flask, and while blowing oxygen from the capillary, at a temperature of 8@℃ and a degree of vacuum of 1 (H1 to 200
The produced water was allowed to ooze out under fO conditions. Following the same procedure as in Example 5, stop the reaction, dilute with -1 hexane, pass through, wash with alkaline water, wash with water, dehydrate, dilute again with rhohexane, remove the solvent, and remove the solvent. , 2251t) A diol monoester and diester mixture was obtained. H.L.O.
When the monoester content of the mixture was measured, it was found to be 66
It was mol%. Next, the mixture 114f was reacted with phosphorus oxychloride 55f (0.56 mol) in exactly the same manner as in Example 5, and the phosphoric acid monoester was isolated.62ft) Colorless transparent non-volatile liquid I got it. The metal compound was subjected to NMIL, elemental analysis (C!: 51.0% (50j
), H28,496 (6,2), O: 50.8% (!5
1,1), P: 9.8% (9,6), however, values within 0 are calculated values. ] It was confirmed from the O droplets that it was acryloyloxydecyl dihydrodiene phosphate. Purity is 91~ from HLO! It turned out to be 5%.

Example 8 In Example 7, 1.10-decanediol was added to 1°12
An experiment was conducted under exactly the same conditions as in Example 7 except that -dodecanediol 260f (1,S mol) was used, and a diol monoester and diester mixture was obtained. H.L.O.
After determining the monoester content with
The q-acid esterification reaction was carried out using a molar equivalent amount of the cough mixture. Separation and purification were performed in exactly the same manner as in Example 5 to obtain a 79fO liquid compound. N of the compound
MB measurement measurement 1 common element [0:5! l, 9% (53,6),
H: 9.0% (8,7), O: 26.1% (zzs)
, Fs 9. 0% (9,2), calculated value using a 2 L square inner needle] and found that it was acryloyl oxide dodecyl dihydrogen phosphate. l
As a result of ILC analysis, the purity was 92-96%.

Examples 9 to 18 and Comparative Examples 1 to 2 Adhesives containing the adhesive monomer of the present invention were prepared in the following manner, and water resistance tests for adhesion to metal were conducted.

Adhesive composition Packaging adhesive monomer 5 parts by weight Methyl methacrylate 95# Benzoyl peroxide 1 #l Packaging material Methyl methacrylate (PIiQ) powder 100 parts by weight Sodium benzenesulfinate 5 #N,N-jetanol -) Luizine 1 # (M and L packaging is a homogeneous solution, L packaging is a mixture of FMM powder and sodium benzene sulfinate and amine powder uniformly mixed and dispersed) 10X10X1wO nickel-chrome A base metal (Nis92
．． 7%) Polish the chip with φ1000 polishing paper and rinse with water.

Sonically cleaned with methyl ethyl ketone. 5 on this chip
■ A piece of dragonfly tape with a φ hole was pasted so that the hole coincided with the center of the abrasive surface. Separately, prepare the same number of 7wφ×15■O stainless steel rods as the nickel-chrome base metal tips, and
Polish the Man〇 Enda painting in the same way.

Washed. One package and one package of the above-mentioned adhesives were packed together and applied with a brush to the alloy chip (Ryuro Tape O hole O part) and stainless steel rod, and adhesive bonding was carried out at No. 91. 9. Add h2o@o@attachment to one adhesive.9. Adhesion 1 hour 9
It was immersed in water at 57°C.

After 24 hours and after 10 days, 10 samples each were taken out and the tensile adhesive strength was measured using an Instron tensile tester, and the average values are shown in Table 1. In addition, the tensile strength is 400#
In the case of /- or more, cohesive failure of the adhesive occurred, and in the case of less than that, interfacial failure occurred mainly at the nickel-chromium alloy surface.

凰1i, (3-0-COO(0111)@0POiH*) When the adhesive monomer of the present invention is used, the initial adhesive strength is very high at 400#/- or more, and after 10 days of immersion in water. However, no decrease in adhesive strength was observed.
73. Known phosphoric acid monoester sotsumer - 1 example Jif,
When carried out in the same manner as above using methacryloyloxyethyl dihydrodiene phosphate (Comparative Example 1)
When the adhesive monomer is not included (Comparative Example 2), the second
11! As shown in Figure 2, when the adhesive sample was immersed in water, the adhesive strength decreased rapidly.

Table 2 Examples 19-20 and Comparative Example 5 Using the adhesive monomers shown in Table 98, two-component adhesives were prepared according to one of the following methods, and the adhesives were used to bind commercially available composite resins to human-ivory. The adhesive strength was measured.

Solution C 2.2'-bis(S-methacryloyloxy-2-7-alxy)phenyl]furopane 40
Weight l5at pentyl glycol dimethacrylate
35 jF adhesive sotsuma! 5 # Benzoyl peroxide 1.5 #2.6
-di-t-butyl-P-cresol (j03
#wI Ethanol 100 parts by weight Sodium benzenesulfinate 4N,
N-getanol-di-toluidine 1.7#
Place the denture molar in a prismatic manner so that the dentin is exposed on the bonding surface.
9 and the ivory square stick (10X10X!S.

-) Prepare. Store these refrigerated in water until just before use. Immediately before use, wipe water from the dentin surface of the denture.
, the dentin image was etched for 1 minute with a 40% aqueous solution of sulfuric acid. Next, it is thoroughly washed with running water, water is evaporated by blowing clean air or nitrogen, and an aluminum strip is wrapped around the side WJ. On the other hand, for ivory sticks, wipe off the moisture on the adhesive surface using commercially available konbujift resin l'-CI RF.
i IF@J (manufactured by Kuraray) was mixed, and this paste was glued to the denture and ivory bonding uniform by sandwiching it between the two. After no bonding time, the sample piece was immersed in water at 57°C and heated for 18 minutes.
The tensile adhesive strength was then measured using an Instron tensile tester (crosshead speed 2/m1x) and the results are shown in Table 5. Seven dentures were used to evaluate one type of adhesive, and the average value of the adhesive strength of the seven dentures was shown.

Table S Applicant: Kuraray Co., Ltd. Agent: Patent Attorney Honda -

Claims (1)

[Claims] (1) General formula (in the formula, - is 5 or 61211 and represents the OII number, and 凰 represents hydrogen or a methyl group) i? (meth)acryloyloxyalkyl dihede a diene phosphate. (2) - is S and 凰 is a methyl group Patent claim OII■1
111 [Umbrella sphate described. (1) The IIO umbrella sumaate according to claim 1, wherein @ is S and 1 is water volume. (4) The umbrella sulfate according to Claim 1, wherein - is 6 and 凰 is a methyl group. (5) Job is 4. The medium sulfate according to claim 1, wherein R is hydrogen. (6) Claim 1 in which the theory is 8 and 凰 is a methyl group
The book sphate mentioned in section. (7) Claim 11 in which ``Job'' is 8, 凰 is ``water'', and ``sou'' is ``sou''.
Phosphate according to item 1. (8)' The phosphate according to claim 1, wherein II is 10 and 凰 is a methyl group. (1) 10% of Sono 1 and 10% of sulfate in claim 1 are hydrogen. Claim 1 in which n is 12 and 凰 is a methyl group
Phosphates listed in Section. The phosphate according to claim 1, wherein u is is 12 and 凰 is hydrogen. A linear O-alkylene diol represented by the general formula HO4-OH,-)110H (in the formula, brittleness is S or an integer up to 61!) is reacted with acrylic acid, and then O-oxychloride is obtained. Phosphate is added to react with the sonoester, then the reaction product OF -O1 is hydrolyzed to form the monoester into a phosphoric acid ester, and then the mixture of the phosphoric acid ester and the diester is converted into cough phosphoric acid. (meth)acryloyloxyalkyl represented by the general formula (in the formula, n is an integer from 5 to 12, and B represents hydrogen or methyl group), which is characterized by separating the ester ■Production method of hydrogen phosphate ．．