JPS6042222B2 - 4-Acryloxethyl trimellitic acid ester and its acid anhydride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel 4-acryloxyethyrytrimeo CH2
-℃H--COO-CH2CH2--OC or H \ / / Relating to lithic acid ester and its acid anhydride.

That is, the gist of the present invention is a 4-acryloxyethyl trimellitic acid ester (hereinafter referred to as the ester compound of the present invention) represented by the formula: )H [1a].

) or its acid anhydride (hereinafter referred to as the anhydride compound of the present invention). The anhydrous compound of the present invention of the above formula [Ib] is:
It is produced by reacting a compound represented by the formula: CH2=CH-COO-CI (2CH2-0H) with trimellitic anhydride or a reactive derivative thereof, usually in a reaction solvent.

The reactive derivatives of trimellitic anhydride include acid halides obtained by reacting trimellitic anhydride with various reaction reagents, such as halogenating agents (thionyl chloride, phosphorus tribromide, etc.), and reactions with alcohols. Examples include active esterified products obtained by reaction with Woodward reagent or Mukaiyama reagent, and products obtained by reaction with other imidazole compounds.

As the reaction solvent, benzene, toluene, xylene, tetrafuran, dioxane, pyridine, hexane, heptane, etc. may be used.

The above reaction may be carried out usually at room temperature or at a temperature below 45°C, preferably below 10°C, for 1 to 1 hour, preferably 3 to 5 hours. In addition, when using the above-mentioned acid halide, it is preferable to use a tertiary amine such as triethylamine or dimethylaniline as a dehydrohalogenating agent. Furthermore, when trimellitic anhydride is used in its free state, an esterification catalyst (p-toluenesulfonic acid, dicyclohexylcarbodiimide, N,N
The reaction can be advantageously proceeded by using a compound (e.g. "-carbodiimidazole).The ester compound of the present invention of the above formula [1a] can be produced by hydrolyzing the anhydrous compound of the present invention in a conventional manner. As described above, the ester compound of the present invention and the anhydrous compound of the present invention are obtained, and these compounds themselves are generally obtained as pale yellow to white crystals.

As this type of α,β-unsaturated alkanoyloxyalkyl trimellitic acid ester or its acid anhydride, for example, 4-methacryloxyethyl trimellitic acid or its acid anhydride represented by the formula: is known. (Refer to Japanese Unexamined Patent Publications No. 54-111 and No. 54-12338).

Such known compounds form adhesives in combination with other vinyl compounds, are mainly used for teeth, metals, and undercoating paints, and are said to exhibit strong peel strength. However, since this compound has a compound with a considerably large chain length and molecular weight bound to the methacryloyl group, the polymerization rate is slow, and it is difficult to polymerize with conventional catalysts and promoters (such as benzoyl peroxide, dimethylaniline, etc.) in the coexistence of other vinyl compounds. , methyl ethyl ketone peroxide, and cobalt naphthenate) tended to not be able to fully demonstrate their performance. Therefore, the present inventors conducted research to improve this point, and surprisingly found that 4-coacryloxyethyl trimellistate acid ester and its acid anhydride were extremely effective, and completed the present invention. I ended up letting it happen. That is, the introduction of the nacryloyl group prevents a decrease in the polymerization rate, and also prevents the polymerization rate from decreasing as described above. It was sufficiently active in media and accelerators, and even when coexisting with other vinyl compounds, the reaction proceeded without any practical problems, and a significant improvement in adhesive performance was observed.

The ester compounds and anhydrous compounds of the present invention can be applied to various types of adhesive compositions.

This adhesive composition comprises: (a) at least one of the ester compound of the present invention and the anhydrous compound of the present invention; (b) at least one polymerizable compound having an ethylenically unsaturated bond;
and (C) at least one polymerization initiator,
Adhesive compositions that are generally cured at room temperature, relatively low temperatures, or by light, have a high adhesive strength, especially on metals, teeth, etc., have a fast curing speed, and also have excellent flexibility and solvent resistance. Overall, it is a well-balanced reactive adhesive composition. Here, the term "adhesive composition" includes adhesives, paints, gap-filling agents, and the like. Note that such a composition does not necessarily have to be a one-component type (that is, a mixture of components a and c at once), but may be, for example, a two-component type in which components a and b are separated, or other multi-component types. It is a liquid type and can be applied sequentially. Examples of the polymerizable compound of component b include (meth)acrylates such as vinyl acetate, acrylonitrile, styrene, α-methylstyrene, (meth)acrylic acid, methyl (meth)acrylate, and ethyl (meth)acrylate, and hydroxyl groups and halogens. Its alkyl side chain substituted products, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate (meta)
Acrylate, 1,3-butylene glycol di(meth)
acrylate, neopentyl glycol di(meth)acrylate, 2,2″-bis(4-(meth)acryloxypropyloxyphenyl)propane, 2,2″-bis(4
-(meth)acryloxyethoxyphenyl)propane,
2,2'-bis(4-(meth)acryloxydiethoxyphenyl)propane, bisphenol A di(meth)acrylate, bisphenol A diglycidyl(meth)acrylate, diallyl phthalate, triallyl cyanurate, trimethylolpropane tri( Reaction of meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, epoxy(meth)acrylate, organic diisocyanate with oxyalkyl (meth)acrylate or oxyalkyl di(meth)acrylate product, the reaction product of a urethane prepolymer (reaction product of an organic diisocyanate and a diol) with a (meth)acrylic ester of an oxyalkanol having at least 2 carbon atoms, containing at least two polymerizable ethylenes. Polymerizable prepolymers containing ethylenically unsaturated groups, reaction products of dibasic carboxylic acids having ethylenically unsaturated groups and dihydric alcohols (i.e. polyesters generally having ethylenically unsaturated groups), etc. It will be done.

(The above (meth)acrylic acid refers to acrylic acid or methacrylic acid, (meth)acrylate refers to acrylate or methacrylate, and (meth)acryloxy refers to acryloxy or methacryloxy, respectively.)
These polymerizable compounds may be used alone or in appropriate combinations, and combinations of styrene, methyl methacrylate and di(meth)acrylate, polymerizable prepolymers, polyesters, etc. are particularly preferred. The blending ratio of component a and component b may be changed as appropriate depending on the purpose of use of the composition, but usually the weight ratio of component a/component b is 111,000.
-115, preferably 11500-1110. If the above weight ratio is less than 11,100, the adhesive effect will be poor, and if it exceeds 115, the water absorption rate will increase and only a polymer with poor water resistance will be obtained, resulting in a decrease in the adhesive effect. It is recognized that there is a tendency towards Examples of the polymerization initiator for component c include benzoyl peroxide, dicrumyl peroxide,
Examples include various peroxides such as isopropyloxydicarbonate and azobisbutyronitrile, but in the case of polymerization at room temperature, tri-n-butylborane, cobalt naphthenate/methyl ethyl ketone peroxide, aromatic tertiary amine/benzoyl peroxide are used. Preferred are known combinations such as.

When polymerizing under ultraviolet or visible light, a combination of ordinary photosensitizers (benzoin, benzoin alkyl ether, benzyl, etc.) and accelerators (p-phenylamine, triethylamine, tributylphosphine, allylthiourea, etc.) is preferred. . The amount of component c to be used is usually selected within the range of about 0.1 to 5% (wt%, same hereinafter) based on the total amount of components a and b. Such compositions essentially contain the above-mentioned components a to c, but appropriate amounts of conventional additives may be added depending on the intended use (adhesive, paint, application as a gap-filling agent).

For example, inorganic fillers (kaolin, talc, clay, calcium carbonate, silica, alumina, aluminosilicate,
(calcium silicate, calcium phosphate, glass, etc.), organic fillers (crushed products of walnut grain, wood, cured thermosetting resin, etc.), composite fillers of the above inorganic fillers and crushed products of cured thermosetting resin, etc. These are usually 1 to 10
A particle size of about 0 μm is used, but if particularly high gloss is required, a fine powder with a particle size of 5 μm or less, preferably 1 μm or less is suitable, and a spherical shape or something close to it is preferable.
As other additive components, modifiers such as wax, paraffin, polymethyl methacrylate, and polystyrene, thickeners, polymerization accelerators, polymerization regulators, and polymerization inhibitors may be used. In addition, when using the above-mentioned inorganic filler, it is preferable to treat it with a usual surface treatment agent (eg, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropylmethoxysilane, etc.).

In addition, in order to obtain a particularly transparent adhesive or gap-filling agent, the refractive index of the copolymer of component a and component b should be
It is desired that the filler material be the same as or similar to that of the various fillers used. When applying the above composition, it is not necessary to use a special solvent, and it is preferable to use component a uniformly dissolved in component b. After dissolving in a solvent (colon, ester, alcohol, pensol, etc.) and applying it to the surface to be adhered and drying it, a composition containing component B and component C is applied and cured by a conventional method. A processing method can also be adopted.

All of the cured films formed in this way can exhibit extremely high adhesion to metals and teeth, and are highly flexible and durable, making them suitable for various uses. Next, Examples and Comparative Examples will be given to demonstrate the present invention. Explain physically.

Note that the present invention is not limited to these Examples at all. The 1-tensile adhesion test in each example was conducted in the following manner. Tensile adhesion test The test was conducted in accordance with JIS K6849, and the metal test piece was a round bar specimen with a diameter of 6. -, and the surface to be adhered is abrasive paper No. 600 (JISR6
252) until glossy, and JIS Kl5O8 (
The sample was thoroughly washed with trichlorethylene (hereinafter abbreviated as treclene) and dried before use.

The acrylic round bar was also tested in the same manner as the metal test specimen, but washing with trichlorene was omitted. In the case of extracted bovine teeth or human teeth, prepare a plane of 6 or more gourds on the enamel or dentin, polish uniformly with 60 sheets of abrasive paper, etch with 30% phosphoric acid aqueous solution for 3 circles and 2 times, wash with water and dry, then proceed as above. A test was conducted using a Shimadzu Autograph IS-1000 at a tensile speed of 1 Tm/min using a Shimadzu Autograph IS-1000 with the round bar test specimens glued together and via an adapter. Note that the unit of the test value is Kg/d. j Example 1 Production of acid anhydride of 4-acryloxyethyl trimellitic acid ester: -Trimellitic anhydride chloride 21.0
Add 50ml of benzene to 150ml of benzene solution of y under ice cooling.
A solution consisting of 11.6V of 112-hydroxyethyl acrylate and 7.9Y of pyridine was added dropwise and allowed to react for 2 hours, and further allowed to react for 2 hours at room temperature.

After the reaction is completed, the precipitated pyridine hydrochloride is separated, and the benzene is distilled off under reduced pressure. N-hexane was added to the residue, cooled, and the precipitated crystals were harvested to obtain the title compound 10 da. Melting point 43.0~45.0°C01R Svectorini (Cm-
1) 1855, 1780 (acid anhydride>C=0), 172
0,1710 (ester)C=0).

NMR vector di(δ) 4.53 (4H, -CH2-
CH2-), 5.83, 6.20 (3H, CH2=CH
-), 8.03, 8.43, 8.55 (3111 aromatic).

Example 2 Production of 4-acryloxyethyl trimellitate: 8 q of the acid anhydride of 4-acryloxyethyl trimellitate obtained in Example 1 was dissolved in tetrahydrofuran, and 10 Da of water was added thereto at room temperature. Stir and leave overnight.

Then, the distillate is removed by heating under reduced pressure and extracted with ethyl ether. After collecting the ether layer, washing with water and drying, ethyl ether was distilled off under reduced pressure and crystallized from n-hexane/benzene to obtain the title compound (yield: 5.2 Da). Melting point 119.5
~122.5°C. The 1R spectrum showed that the absorption of acid anhydride disappeared and the absorption of carboxylic acid appeared at 1695cw1-1.

Example 3 2,2″-bis(p-2″-hydroxy-3″
- Methacryloxypropoxyphenyl) propane (hereinafter abbreviated as RBIS-GMAj) (to) parts (by weight, hereinafter the same), triethylene glycol dimethacrylate (hereinafter abbreviated as ]q) 65 parts, 4-acryloxyethyl An adhesive is prepared by blending 4 parts of an acid anhydride of trimellitic acid ester, 0.5 part of benzoyl peroxide (hereinafter abbreviated as RBpOJ), and 0.5 part of dimethylaniline.

Appropriate pretreatment (triclean cleaning) was applied to the surfaces to be bonded of various round rod test specimens, and the above adhesive composition was applied and bonded. 2. After being left in air or water at 3C for 1 day and 1 week. and then subjected to a tensile adhesion test.

The results are shown in Table 1. Comparative Example 1rBIS-GMAJ (9
) part, R3GJ7 pro, RBpOJO. The same test as in Example 3 was conducted using an adhesive consisting of 5 parts of dimethylaniline and 0.5 parts of dimethylaniline, and the results are also listed in Table 1.

Example 4 0BIS-GMA. 7G$, ethylene glycol dimethacrylate (hereinafter referred to as.

1 Gyo) 2 Kusaka methyl methacrylate (hereinafter referred to as RM)
An adhesive is prepared by blending 5 parts of MAJ, 4 parts of acid anhydride of 4-acryloxyethyl trimellitic acid ester, 0.5 part of 1BP0, and 0.5 part of dimethylaniline.

Appropriate pretreatment (triclene cleaning, phosphoric acid treatment (treatment with 30% phosphoric acid for 3 times and 2 hours, washing with water and drying)) was performed on the surface to be bonded of various round rod test specimens, and the above adhesive was applied to this. After bonding, the samples were left in air or water at 23° C. for one day or one week, and then subjected to a tensile adhesion test. The results are shown in Table 2. Comparative Example 2 rBIS-GMA 7 JlG 25 parts, 1 MMA 5
part, 0.5 part of 1BP0 and 0.5 part of dimethylaniline
A test similar to that in Example 4 was conducted using an adhesive consisting of 2 parts, and the results are also listed in Table 2.

Example 5 Instead of adhering the metal rod and acrylic rod test specimens with an adhesive as in Example 4, acrylic was directly polymerized onto the metal rod and a tensile test was conducted using polymethyl methacrylate (hereinafter referred to as polymethyl methacrylate). , RPMMAJ) 99.5 parts and 1BP0. 2 parts of a mixture of 0.5 parts of J and RMMAJ
Co., Ltd., 5 parts of trimethylolpropane trimethacrylate (hereinafter abbreviated as RTMP) and 1 part of a mixture of 5 parts of acid anhydride of 4-acryloxyethyl trimellitic acid ester are mixed, and the metal rod and the acrylic are mixed in advance. Insert each into a plaster mold with a metal frame that has an empty space for filling, and
An adhesion test is conducted using a specimen that has been heated in 0'C water for 1 hour to polymerize acrylic.

The results are shown in Table 3. Comparative Example 3 In Example 5, 99.5 parts of RpMrvAJ and R
BpOJO. Adhesion tests were conducted under similar conditions, except that a mixture of 2 parts of a 5 part mixture and 1 part of a mixture of 9.5 parts of RMMAJ and 5 parts of RTMPT was used, and the results are also listed in Table 3.

Comparative Example 4 An adhesion test was conducted under the same conditions as in Example 5, except that the acid anhydride of 4-methacryloxyethyl trimellitic acid ester was used instead of the acid anhydride of 4-acryloxyethyl trimellitic acid ester. , the results are also listed in Table 3.

Example 6 In conducting an adhesion test similar to Example 4, RPMMAJ
65 parts, RMMA 33 parts, 1TMPT 2 parts, RBP
An adhesion test is carried out using a mixture of 0.4 part of O, 0.1 part of dimethyl para-toluidine, and 2 parts of acid anhydride of 4-acryloxyethyl trimellitic acid ester as an adhesive composition.

The results are shown in Table 4. Comparative Example 5 The composition of Example 6 except that the acid anhydride of 4-acryloxyethyl trimellitic acid ester was removed, that is, 5PMMA. j65 copies.

MMAJ 33rd Division, 3rTMP1'J2 Division, RBPOJ
O. Using a mixture of 4 parts of dimethyl p-toluidine and 0.1 part of dimethyl p-toluidine as an adhesive composition, an adhesion test was conducted under the same conditions. The results are also listed in Table 4. Comparative Example 6 An adhesion test was conducted under the same conditions as in Example 6, except that the acid anhydride of 4-acryloxyethyl trimellitate was used instead of the acid anhydride of 4-acryloxyethyl trimellitate. The results are also listed in Table 4.

Example 7 The clasp of a local denture with a wire clasp fell off during use, and in order to repair it, the clasp was polished to give a fresh surface and an acetone solution of 5% 4-acryloxyethyl trimellitic acid anhydride was used. After applying it twice with a brush and drying it, I repaired it with instant polymerization resin (trade name 7 Kuitsukurejinyo, manufactured by Shofu Toto Seizo Co., Ltd.) according to the usual method, and then put it on the patient and used it, but no abnormality was noticed even after 6 months. I couldn't help it.

Comparative Example 7 Prior to performing the treatment of Example 7 using the same local denture as Example 7, the patient used it after repairing it using the conventional method, that is, using the product name 1 Kuitsukurejinyo, but after 3 months, the metal and resin at the repaired area were not bonded. There was a gap between the parts, and the clasp became loose.

Claims (1)

[Claims] 1. 4-Acryloxethyl trimellistate ester or its acid anhydride represented by the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼.