JPS6042223B2 - 4-[2-(meth)acryloyloxypropyl] trimellitic acid and its acid anhydride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel 4-[2-(meth)acryloyloxypropyl] trimellitic acid and its acid anhydride.

That is, the gist of the present invention is the formula: ] ) COOH CH2-C(〇O--CH2CH-AχD] [2] [[
I] [In the formula, R represents hydrogen or a methyl group.

However, an acid anhydride may be formed between two carboxyl groups on the benzene ring. ] 4-[2-(meth)acryloyloxypropyl trimellitic acid] (hereinafter referred to as the ester compound of the present invention).

) or its acid anhydride (hereinafter referred to as the anhydride compound of the present invention). Specific examples of the ester compound of the present invention or anhydrous compound of the present invention of the above formula [I] are listed below. CH
3CH211COOH CHCCOO-CHCH-OCO2CH3CH3; 1CO CH2-C-C⊥(H2CH-()C℃2)o' CH
.

-CH(01°CH.CH-()C) The anhydrous compound of the present invention has the formula [wherein, R has the same meaning as above].

It is produced by reacting the compound represented by ] with trimellitic anhydride or a reactive derivative thereof, usually in a reaction solvent.

Examples of the above [older compounds] include acryloxypropyl alcohol-2 (or 2-hydroxypropyl acrylate) and methacryloxypropyl alcohol-2 (or 2-hydroxypropyl methacrylate).

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

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

The above reaction is usually carried out at room temperature or at a temperature below 45°C, preferably at a temperature below 10'C. It may be carried out for a period of time, preferably 3 to 5 hours. In addition, when using the above acid halide, triethylamine or dimethylanidine is used as a dehydrohalogenating agent. Preference is given to using tertiary amines such as phosphorus. Furthermore, when trimellitic anhydride is used in its free state, an esterification catalyst (p-toluenesulfonic acid, dicyclohexylcarbodiimide, N
, N-carbodiimidazole, etc.), the reaction can proceed advantageously. The ester compound of the present invention is produced by hydrolyzing the anhydrous compound of the present invention by a conventional method. The ester compound of the present invention and the anhydrous compound of the present invention are obtained as described above, and these compounds themselves generally exhibit a pale yellow to white oily or crystalline form.

The ester compound and anhydrous compound of the present invention can be applied to various 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 of the polymerizable compounds having an ethylenically unsaturated bond, and (c) a polymerization initiator. An adhesive composition that is generally cured at room temperature or relatively low temperature or by light, has a high adhesive strength to metals, teeth, etc., has a fast curing speed, and is flexible. It has excellent properties and solvent resistance, and is a well-balanced reactive adhesive composition as a whole. Here, the term "adhesive composition" includes adhesives, paints, gap-filling agents, and the like. In addition,
Such a composition does not necessarily have to be a one-component type (i.e., a mixture of a-c components); for example, a.
A two-component type in which component and b component are separated, and other multi-component types can be applied sequentially.

The polymerizable compound of component b is, for example, vinyl acetate, acrylonitrile, styrene, α-methylstyrene, (meth)acrylic acid, methyl (meth)acrylate,
(Meth)acrylates such as ethyl (meth)acrylate and their alkyl side chain substituted products with hydroxyl groups or halogens, 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, 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(meth)acrylate, trimethylolethane tri(meth)acrylate , tetramethylolmethanetetra(meth)acrylate, epoxy(meth)acrylate, reaction product of organic diisocyanate and oxyalkyl (meth)acrylate or oxyalkyl di(meth)acrylate, urethane prepolymer (reaction product of organic diisocyanate and diol) A polymerizable prepolymer containing at least two polymerizable ethylenically unsaturated groups, which is a reaction product of (meth)acrylic acid ester of an oxyalkanol having at least 2 carbon atoms, ethylene A reaction product of a dibasic carboxylic acid having an ethylenically unsaturated group and a dihydric alcohol (that is, generally a polyester having an ethylenically unsaturated group), and the like.

(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 various peroxides such as benzoyl peroxide, dicumyl peroxide, isopropyl oxydicarbonate, and azobisbutyronitrile. Butyl borane, cobalt naphthenate/methyl ethyl ketone peroxide, tertiary aromatic
Preferred are known combinations such as amine/benzoyl peroxide. 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 used is usually about 0.1 to 0.1 to the total amount of components a and b.
It may be selected within a range of 5% (weight %, hereinafter the same). 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, gap-filling agent, etc.).

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 more 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.).

Furthermore, in order to obtain particularly transparent adhesives or gap-filling agents, it is desirable that the refractive index of the copolymer of component a and component b be the same as or close to that of the various fillers used. It will be done. When applying the above composition, it is not necessary to use a special solvent, and it is preferable to use it in a state where component a is uniformly dissolved in component b. (ketones, esters, alcohols, pensoles, etc.) and applied to the surface to be adhered and dried, then a composition containing components B and C is applied thereto and hardened by a conventional method. method can also be adopted.

All of the cured films formed in this manner can exhibit extremely high adhesion to metals and teeth, and are highly flexible and durable, making them suitable for various uses. Next, the present invention will be specifically explained with reference to Examples and Comparative Examples.

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. The metal specimen was a round bar specimen with a diameter of 6.0 Tm, and the surface to be adhered was coated with 60 square meters of abrasive paper (JISR
6252) until glossy, JIS Kl5O8
(Trichlorethylene, hereinafter abbreviated as Treklene) was thoroughly washed and dried before use.

The acrylic round bar and ivory round bar were also used as metal test specimens, but
Triclean washing was omitted. In the case of extracted bovine teeth or dentures, a flat surface of 6 Trrm or more is provided on the enamel or dentin, polished uniformly with 60 m of abrasive paper, etched for 30 seconds with a 30% phosphoric acid aqueous solution, washed with water and dried, and then the above round bar specimen Shimadzu Autograph IS
-1000, tensile speed 17077! /min. Note that the unit of the test value is K9/C chisel.
Example 1 Production of acid anhydride of 4-(2-methacryloyloxypropyl) trimellitate: -To a solution of 21.0 y of trimellitic anhydride chloride in 150 ml of benzene, 2
A solution consisting of 14.4q1 -hydroxypropyl methacrylate, 7.9y pyridine and 50mt benzene was added dropwise at room temperature and allowed to react for 4 hours.

After separating the precipitated pyridine hydrochloride, benzene is distilled off under reduced pressure. N-hexane is added to the residue, and the precipitated crystals are filtered off to obtain the title compound 14.7y. This is benzene/n-hexane! When recrystallized, the melting point is 90.0~
It showed 93.0°C. 1R Svectorni (C!Tt-
1) 1850, 1780 (acid anhydride) C=O), 1720 (
Ester':, C=O).

NMR vector density (δ) 35.
50, 6.00 (2H, CH2=), 8.00, 8.4
2,8.534f((31(, aromatic ring).

Example 2 Production of 4-(2-methacryloyloxypropyl) trimellitate: 5 g of the acid anhydride obtained in Example 1 was dissolved in tetrahydrofuran, 10 y of water was added, stirred at room temperature, and left overnight.

Then, the distillate is removed by heating under reduced pressure, and the mixture is extracted with ethyl ether. After the ether layer was collected, washed with water and dried, ethyl ether was distilled off under reduced pressure and crystallized from n-hexane/benzene to obtain the title compound. Yield 3y, melting point 97-99.
5℃. The 1R spectrum showed that the absorption of acid anhydride disappeared and the absorption of carboxylic acid appeared at 1695 cm-1.

Example 3 Production of acid anhydride of 4-(2-methacryloyloxypropyl) trimellitate: - Into a solution of 21.0 Da of trimellitic anhydride chloride in 150 ml of benzene,
A solution consisting of 14.0y of 2-hydroxypropyl acrylate, 7.5y of pyridine and 50ml of benzene was added dropwise at room temperature and allowed to react for 4 hours.

After the precipitated pyridine hydrochloride is separated, benzene is distilled off under reduced pressure to obtain the title compound. Yield 17y, yellow oil. IR Svectorini (C7l-1) 1850, 1780 (acid anhydride>C=0), 1720 (
ester]C=0).

NMR vector density (δ) 5.85, 6.20 (3H, CH2=CH-), 8.0
3,8.43,8.56 (3H1 aromatic ring).

Example 4 2,2″-bis(p-7-hydroxy-3′-methacryloxypropoxyphenyl)propane (hereinafter referred to as RBIS
7 parts by weight (abbreviated as GMAj), 25 parts of triethylene glycol dimethacrylate (hereinafter abbreviated as R3GJ), 4 parts of acid anhydride of 4-(2-methacryloyloxypropyl) trimellitic acid, An adhesive is prepared by blending 0.5 part of benzoyl oxide (hereinafter abbreviated as JBPO) and 0.5 part of dimethylaniline.

The surfaces of various round rod test specimens to be adhered were cleaned with Triclean, the above-mentioned adhesive was applied thereto to adhere them, and the specimens were left in air or water at 23° C. for 1 day or 1 week, and subjected to a tension adhesion test.

The results are shown in Table 1. Comparative Example 1 A test similar to Example 4 was conducted using an adhesive consisting of 0.5 parts of BPO and 0.5 parts of dimethylaniline, and the results were as follows. are also listed in Table 1.

Example 5 35 parts of 2,2″-bis(4-methacryloxyethoxyphenyl)propane (hereinafter abbreviated as R2E), -2,2
35 parts of ``-bis(4-methacryloxydiethoxyphenyl)propane (hereinafter abbreviated as R4El), ethylene glycol dimethacrylate (hereinafter abbreviated as 11G), 0.5 part of 1BP0, dimethyl para-toluidine 0.
5 parts of acid anhydride of 4-(2-methacryloyloxypropyl) trimellitate and silica stone (average particle size 5μ)
) Adhesion was carried out in the same manner as in Example 4 using 315 parts of the composition as an adhesive, and the samples were left in air or water at 23°C for 1 day and 1 week, and subjected to a tensile adhesion test.

The results are shown in Table 2. Comparative Example 2 An adhesion test was conducted in the same manner as in Example 5 using the composition of the present invention without the acid anhydride, and the results are also listed in Table 2.

Example 6 65 parts of polymethyl methacrylate, 34 parts of methyl methacrylate, RBpOJO. A mixture of 4 parts of dimethyl paratoluidine, 0 parts of dimethyl paratoluidine and 0 parts was used as an adhesive composition, and a 5% acetone solution of 4-(2-acryloxypropyl trimellitate) was applied to a metal test piece to perform adhesion according to the test in Example 5. Apply to the surface to be adhered and dry.

The results are shown in Table 2. Comparative Example 3 When applying the composition of Example 6, it was adhered and tested in the same manner as in Example 6 without applying the 5% acetone solution of the ester compound of the present invention.

The results are also listed in Table 2. Example 7 68 parts of polymethyl methacrylate, 3 parts of methyl methacrylate Using a mixture of 3 parts of 4-(2-methacryloyloxypropyl) trimellitate as an adhesive composition, the method of Example 5 was applied mutatis mutandis to prepare a test specimen by heating and pressurizing it at 100°C for 20 minutes, and after 1 day, it was subjected to a tensile test. I went to

The results are shown in Table 3. Comparative Example 4 In Example 7, the ester compound of the present invention was excluded. A similar test was conducted using the same composition.

The results are also listed in Table 3. Example 8 68 parts of polymethyl methacrylate, 3 parts of methyl methacrylate, mostly V. ,.

BPOJO. 3 parts, dimethyl paratol 4 idine O numabe,
Using a mixture of 3 parts of 4-(2-methacryloyloxypropyl) trimellitic acid as an adhesive composition, the method of Example 5 was applied mutatis mutandis to prepare test specimens under pressure at room temperature, and a tensile test was conducted one day later. The results are shown in Table 3. Comparative Example 5 A test was conducted in the same manner as in Example 8 except that the ester compound of the present invention was omitted.

The results are also listed in Table 3. υExample 9 When making metal base dentures, a nickel alloy (product name 1 Dent nickel manufactured by Shofu 6J Tooth Manufacturing Co., Ltd., Ni 63%, Crl 5%, MO5
%, Mn 5%, others 12%), and 4-(2-methacryloyloxypropyl trimellitate) was added to 1 (1) part of common liquid as a floor resin (trade name 1 Urbanyo, manufactured by Shofu Toto Seizo Co., Ltd.). ) using a mixture of 5 parts of acid anhydride, make a denture according to the conventional method, and attach it to the patient.
The condition of the product was examined after 6 months of use, and no abnormalities were observed at the joint between the resin and metal.

Comparative Example 6 When making a metal base denture, dentures were made using the product name 0 Dentnikkeyo and the product name 1 Urbano was used as the base resin, and the dentures were made according to the usual method and the condition was examined after 6 months of wearing the dentures on a patient. However, there was a small gap in the joint between the resin and metal, and that part had turned black.

Example 10 In Comparative Example 6, the resin was removed from the defective part of the resin-metal joint, and a fresh surface of the metal was exposed.
A 5% methyl methacrylate solution of 4-(2-methacryloyloxypropyl) trimellitate was applied and dried, and dental instant polymerization resin (trade name: 0 Quick Resin J, manufactured by Shofu Toto Seizo Co., Ltd.) was applied by brush according to the usual method. After the device was repaired according to the law, it was put back on the patient and used again, but no abnormalities were found after 6 months.

Claims (1)

[Claims] 1 Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents hydrogen or a methyl group. However, an acid anhydride may be formed between two carboxyl groups on the benzene ring. ] trimellitic acid 4-[2-(meth)acryloyloxypropyl] or its acid anhydride.