JP7570182B2 - Polymerizable composition and polymerizable kit - Google Patents

Description

The present invention relates to a polymerizable composition and a polymerizable kit.

It has been known to prepare a two-component adhesive (kit) from a polymerizable composition containing a polymerizable monomer and a complex generated from an organoborane and an amine, and a decomplexing agent (see, for example, Examples 2, 4 to 14, and 17 to 20 of Patent Document 1 below).

In the adhesive described in Patent Document 1, when the decomplexing agent reacts with the complex during use, an organoborane is generated from the complex through a decomplexing reaction of the complex, and this organoborane functions as a polymerization initiator, polymerizing the polymerizable monomer. This causes the adhesive to adhere to the adherend.

JP 2017-141423 A

However, in the above-mentioned examples of Patent Document 1, no particular consideration was given to good aesthetics, and it was found that, for example, an adhesive (composition) to which ascorbic acid was added as a third component had excellent storage stability, but the color tone changed and the aesthetics were impaired.

In recent years, polymerizable compositions are required to have both good aesthetics and excellent stability depending on the application and purpose.

However, the polymerizable composition described in Patent Document 1 may not satisfy the above requirements.

The present invention provides a polymerizable composition and a polymerizable kit that can achieve both good aesthetics and excellent stability.

The present invention (1) includes a polymerizable composition that contains a polymerizable monomer that does not have an acidic group, a complex prepared from raw materials that include an organoborane and a primary amine compound, and an alkoxy group-primary amino group-containing compound that contains an alkoxy group and a primary amino group.

The present invention (2) includes the polymerizable composition according to (1), in which the molar ratio of the primary amino group to 1 molar part of the complex is 2.0 molar parts or more and 5.0 molar parts or more.

The present invention (3) includes the polymerizable composition according to (1) or (2), wherein the alkoxy group-primary amino group-containing compound is R ^A O-R ^B -NH ₂ (wherein R ^A is an alkyl group having 1 to 6 carbon atoms, and R ^B is an alkylene group having 2 to 9 carbon atoms).

The present invention (4) includes the polymerizable composition according to any one of (1) to (3), in which the alkoxy group has a branched alkyl portion having 3 to 6 carbon atoms.

The present invention (5) includes the polymerizable composition according to any one of (1) to (4), in which the polymerizable monomer contains a (meth)acryloyl group.

The present invention (6) includes the polymerizable composition according to any one of (1) to (5), in which the polymerizable monomer is monofunctional.

The present invention (7) includes the polymerizable composition according to any one of (1) to (6), in which the polymerizable monomer is an ester of an alcohol containing an oxygen-containing heterocycle and (meth)acrylic acid.

The present invention (8) includes the polymerizable composition according to (7), in which the polymerizable monomer is any one selected from the group consisting of tetrahydrofurfuryl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, and (5-ethyl-1,3-dioxane-5-yl)methyl (meth)acrylate.

The present invention (9) includes the polymerizable composition according to any one of (1) to (8), in which the primary amine compound further contains an alkoxy group.

The present invention (10) includes a polymerizable kit having the polymerizable composition according to any one of (1) to (9) and a decomplexing agent.

The polymerizable composition and polymerizable kit of the present invention can achieve both good aesthetics and excellent stability.

(Polymerizable composition)
The polymerizable composition of the present invention contains a polymerizable monomer, a complex, and an alkoxy group-primary amino group-containing compound.

The polymerizable monomer does not contain an acidic group. Examples of the acidic group include carboxylic acid groups such as carboxyl groups and carboxylic anhydride groups, phosphoric acid groups, thiophosphoric acid groups, pyrophosphoric acid groups, sulfonic acid groups, and phosphonic acid groups.

A polymerizable monomer that does not contain an acidic group, for example, contains one or more (meth)acryloyl groups in the molecule. Preferably, the polymerizable monomer contains one (meth)acryloyl group. Hereinafter, the (meth)acryloyl group means a methacryloyl group (CH ₂ ═C(CH ₃ )CO—) and/or an acryloyl group (CH ₂ ═CHCO—). The usage of "(meth)acry..." is the same.

A polymerizable monomer containing a single (meth)acryloyl group is a monofunctional monomer. Examples of such polymerizable monomers include (meth)acrylates.

Examples of (meth)acrylates include esters of (meth)acrylic acid and alkanols having 1 to 10 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, and decyl (meth)acrylate. From the viewpoint of ensuring even better stability, preferred are esters of (meth)acrylic acid and alkanols having 1 to 3 carbon atoms, and more preferred are methyl (meth)acrylate.

As the (meth)acrylate, there may be mentioned an ester of an alcohol containing a heterocycle containing oxygen and (meth)acrylic acid. The number of oxygen atoms contained in the heterocycle is 1 or 2 or more, preferably 1 or 2. The number of atoms forming the heterocycle is, for example, 3 or more, preferably 4 or more, and for example, 7 or less, preferably 6 or less. The carbons forming the heterocycle may be substituted with methyl and/or ethyl. As the alcohol containing a heterocycle containing oxygen, there may be mentioned, for example, tetrahydrofurfuryl alcohol, 3-ethyl-3-oxetanemethanol, (2-methyl-2-ethyl-1,3-dioxolane)methanol, (5-ethyl-1,3-dioxane)methanol, and the like. Specific examples of such (meth)acrylates include tetrahydrofurfuryl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (5-ethyl-1,3-dioxane-5-yl)methyl (meth)acrylate, etc. Of these, preferred are tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, and (5-ethyl-1,3-dioxane-5-yl)methyl (meth)acrylate.

Further examples of (meth)acrylates include tetramethylpiperidinyl (meth)acrylate (more specifically, 2,2,6,6-tetramethyl-4-piperidinyl (meth)acrylate) and hydroxyalkyl (meth)acrylates (e.g., 2-hydroxyethyl acrylate).

A polymerizable monomer containing multiple (meth)acryloyl groups is a polyfunctional monomer, also referred to as a crosslinkable monomer. Examples of such polymerizable monomers include esters of polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, and trimethylolpropane with (meth)acrylic acid and/or di(meth)acrylic acid. Specific examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. Preferably, triethylene glycol di(meth)acrylate is used.

The polymerizable monomers can be used alone or in combination. Specifically, monofunctional monomers and polyfunctional monomers (crosslinkable monomers) can be used alone or in combination.

The proportion of the polymerizable monomer in the polymerizable composition is, for example, 60 mol% or more, preferably 75 mol% or more, and, for example, 99 mol% or less, preferably 95 mol% or less. The molar proportion of the polymerizable monomer per 1 molar part of the complex is, for example, 10 mol parts or more, preferably 20 mol parts or more, and, for example, 200 mol parts or less, preferably 100 mol parts or less.

The polymerizable monomers in the polymerizable composition can be identified and quantified by known techniques, such as high performance liquid chromatography (HPLC), nuclear magnetic resonance (NMR), and gas chromatography-mass spectrometry (GC-MS).

(Complex)
The complex is prepared from raw materials including an organoborane and a primary amine compound.

(Organoborane)
The organoborane is represented by, for example, _BR3 . In _BR3 , R may be the same or different from each other. Examples of R include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a cycloalkyl or cycloalkenyl group having 3 to 20 carbon atoms. An alkyl group is preferable.

Specific examples of organoboranes include trialkylboranes having 1 to 20 carbon atoms, such as trimethylborane, triethylborane, tripropylborane, and tributylborane; arylboranes having 6 to 20 carbon atoms (e.g., triphenylborane); and cycloalkylboranes or cycloalkenylboranes having 3 to 20 carbon atoms (e.g., tri(cyclohexyl)borane). As organoboranes, trialkylboranes are preferred, more preferably trialkylboranes having 1 to 10 carbon atoms, even more preferably trialkylboranes having 2 to 8 carbon atoms, and particularly preferably trialkylboranes having 3 to 5 carbon atoms from the viewpoint of ensuring even better stability.

Preferably, the trialkylborane is tributylborane. Examples of tributylborane include tri-n-butylborane, tri-sec-butylborane, and tri-tert-butylborane, and preferably tri-n-butylborane.

A single type of organoborane can be used, or multiple types can be used in combination. It is preferable to use a single type.

The ratio of organoborane is adjusted so that the number of moles of organoborane and the number of moles of primary amino groups in the primary amine compound are in a predetermined ratio described below.

(Primary amine compound)
The primary amine compound has one or more primary amino groups (-HN ₂ ) in the molecule. Furthermore, the primary amine compound may contain, in addition to the primary amino group, for example, one or more secondary amino groups and/or alkoxy groups (methoxy, ethoxy, propoxy, etc.) in the molecule.

Examples of primary amine compounds include (1) a first primary amine compound that does not contain a secondary amino group or an alkoxy group but does contain a primary amino group, (2) a second primary amine compound that does not contain an alkoxy group but contains a primary amino group and a secondary amino group, (3) a third primary amine compound that does not contain a secondary amino group but contains an alkoxy group and a primary amino group (corresponding to an alkoxy group-primary amino group-containing compound), and (4) a fourth primary amine compound that contains a primary amino group, a secondary amino group, and an alkoxy group.

(1) Examples of the first primary amine compound include monoamines such as aliphatic monoamines such as ethylamine, butylamine, hexylamine, octylamine, and benzylamine; diamines such as aliphatic diamines such as 1,2-diaminoethane, 1,3-diaminopropane, 1,5-diaminopentane, 1,6-diaminohexane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, and 3-methyl-1,5-diaminopentane; and alicyclic diamines such as isophoronediamine. Diamines are preferred, aliphatic diamines are more preferred, and 1,3-diaminopropane is even more preferred.

(2) Examples of the second primary amine compound include triamines such as aliphatic triamines such as diethylenetriamine and dipropylenetriamine, and tetraamines such as aliphatic tetraamines such as triethylenetetraamine. Preferably, triamines are used, more preferably aliphatic triamines, and even more preferably diethylenetriamine.

(3) The third primary amine compound is an alkoxy group-primary amino group-containing compound, for example, represented by R ^A O-R ^B -NH ₂ .

In the formula, R 1 ^A is an alkyl group having 1 to 6 carbon atoms, and R 1 ^B is an alkylene group having 2 to 9 carbon atoms.

Specific examples of the alkyl group represented by R ^A include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, sec-pentyl, 3-pentyl, tert-pentyl, hexyl, and isohexyl.

As the alkyl group, preferably, a branched alkyl group is used, and specific examples thereof include isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, sec-pentyl, 3-pentyl, tert-pentyl, and isohexyl. Preferably, isobutyl is used.

Also preferably, the alkyl group is methyl.

The alkylene group represented by R ^B is preferably a linear alkylene group (polymethylene group) having 2 to 9 carbon atoms, such as methylene, ethylene (dimethylene), propylene (trimethylene), butylene (tetramethylene), pentylene (pentamethylene), hexylene (hexamethylene), heptylene (heptamethylene), octylene (octamethylene), or nonylene (nonamethylene), more preferably a linear alkylene group having 2 to 5 carbon atoms, and even more preferably propylene.

Specific examples of the (3) third primary amine compound include methoxy-alkylamines such as methoxyethylamine, methoxypropylamine, and methoxybutylamine; ethoxy-alkylamines such as ethoxypropylamine; propoxy-alkylamines such as propoxymethylamine, propoxyethylamine, propoxypropylamine, and propoxybutylamine; alkoxy-alkylamines having 2 or more and 5 or less carbon atoms in the alkyl portion, such as butoxy-alkylamines, pentyloxy-alkylamines, and hexyloxy-alkylamines. From the viewpoint of stability, preferred examples include methoxy-alkylamines having 2 or more and 5 or less carbon atoms in the alkyl portion, and propoxy-alkylamines having 2 or more and 5 or less carbon atoms in the alkyl portion.

Methoxypropylamines having an alkyl portion with 2 to 5 carbon atoms are preferably 3-methoxypropylamine, methoxyisopropylamine, etc., and more preferably 3-methoxypropylamine.

Propoxy-alkylamines having an alkyl portion with 2 to 5 carbon atoms are preferably propoxypropylamine. Specific examples of propoxypropylamine include 3-propoxypropylamine and 3-isopropoxypropylamine, and preferably 3-isopropoxypropylamine.

(4) Examples of the fourth primary amine compound include N-methoxymethyl-1,3,5-triazine-2,4,6-triamine.

Preferably, the primary amine compound is (1) a first primary amine compound, (2) a second primary amine compound, or (3) a third primary amine compound (an alkoxy group-primary amino group-containing compound). From the viewpoint of ensuring even better stability, more preferably, the primary amine compound is (1) a first primary amine compound, (3) a third primary amine compound, or even more preferably, the third primary amine compound is (3).

The ratio of the primary amine compound is adjusted so that the number of moles of the organoborane and the number of moles of the primary amino groups in the primary amine compound are in a predetermined ratio described below.

The raw materials may contain appropriate amounts of known additives as long as they do not impair the effects of the present invention.

On the other hand, preferably, the raw material contains only an organoborane and a primary amine compound. In other words, preferably, the raw material does not contain any additives and is composed of an organoborane and a primary amine compound.

The method for preparing (synthesizing) the complex from the raw materials will be described later.

The proportion of the complex in the polymerizable composition is, for example, 0.1 mol% or more, preferably 1 mol% or more, and, for example, 10 mol% or less, preferably 5 mol% or less.

The complexes in the polymerizable composition can be identified and quantified by known methods, such as HPLC using a differential refractometer or a UV-Vis (ultraviolet-visible) detector, elemental analysis based on the combustion method, and UV-Vis (ultraviolet-visible) analysis.

The alkoxy group-primary amino group-containing compound is a stabilizer that inhibits decomposition of the complex before use (or during storage) of the polymerizable composition, stabilizing the complex and thereby inhibiting the reaction of the polymerizable monomer.

The alkoxy group-primary amino group-containing compound contains an alkoxy group and a primary amino group. Preferably, the alkoxy group-primary amino group-containing compound is similar to the (3) third primary amine compound (alkoxy group-primary amino group-containing compound) exemplified as the primary amine compound, and is appropriately selected from the (3) third primary amine compound.

More preferably, when the primary amine compound is the (3) third primary amine compound, the alkoxy group-primary amino group-containing compound is the (3) third primary amine compound of the same type. Specifically, when the primary amine compound is 3-isopropoxypropylamine, the alkoxy group-primary amino group-containing compound is 3-isopropoxypropylamine. The above selection simplifies the manufacturing method.

The molar proportion of the alkoxy group-primary amino group-containing compound in the polymerizable composition depends on the number of primary amino groups in the alkoxy group-primary amino group-containing compound, but is, for example, 1 mol% or more, preferably 3 mol% or more, more preferably 7 mol% or more, and is, for example, 25 mol% or less, preferably 20 mol% or less.

The molar ratio of the primary amino group of the alkoxy group-primary amino group-containing compound to 1 molar part of the complex is, for example, 0.5 molar parts or more, preferably 1.0 molar parts or more, more preferably 2.0 molar parts or more, and even more preferably 4.0 molar parts or more, and is, for example, 20 molar parts or less, preferably 10 molar parts or less, more preferably 7.0 molar parts or less, and even more preferably 5.0 molar parts or less.

If the molar ratio of primary amino groups per molar part of the complex is equal to or greater than the lower limit described above, or equal to or less than the upper limit described above, the stability of the polymerizable composition can be further improved.

The identification and quantification of the alkoxy group-primary amino group-containing compound in the polymerizable composition can be carried out by known methods, such as HPLC using a differential refractometer or a UV-Vis (ultraviolet-visible spectroscopy) detector, UV-Vis (ultraviolet-visible spectroscopy) analysis, and elemental analysis based on the combustion method.

The polymerizable composition may contain known additives in appropriate proportions. Examples of additives include fillers, polymerization inhibitors, and other stabilizers. These additives are described, for example, in JP 2017-141423 A.

(Method of Preparing Polymerizable Composition)
Next, a method for preparing the polymerizable composition will be described.

In this method, the polymerizable monomer, the complex, the alkoxy group-primary amino group-containing compound, and additives that are added as needed are mixed in the ratios described above.

The complex is prepared (synthesized) by a known method, and is described in detail, for example, in JP 2017-141423 A. Specifically, an organoborane and a primary amine compound are mixed. In this case, the number of moles of the primary amino group of the primary amine compound per mole of the organoborane is, for example, 1 or more, preferably more than 1 from the viewpoint of ensuring the reaction of the organoborane, more preferably 1.2 or more, even more preferably 1.5 or more, and for example, 5 or less, more preferably 3 or less.

One mole part of organoborane reacts with one mole part of a primary amino group to produce one mole part of a complex, but even if there is any excess primary amine compound, the excess primary amine compound is removed in the solvent removal step described below, and essentially no primary amine compound remains.

In the above blending, a solvent can be blended in an appropriate ratio. Examples of the solvent include ethers such as tetrahydrofuran and diethyl ether, and low molecular weight alkanes such as hexane and heptane.

Specifically, a solvent solution is prepared by dissolving an organoborane in a solvent. Then, the solvent solution is mixed with a primary amine compound. This produces a complex.

Then, the solvent is removed. At this time, the remaining primary amine compound is removed together with the solvent.

(Polymerizable kit)
This polymerizable composition is included in a polymerizable kit together with a decomplexing agent. That is, the polymerizable kit includes a polymerizable composition and a decomplexing agent. More specifically, the polymerizable kit includes a polymerizable composition and a decomplexing agent separately. In detail, in the polymerizable kit, the polymerizable composition and the decomplexing agent are separately prepared as a two-component adhesive until the adherend is bonded as an adhesive, and the polymerizable composition and the decomplexing agent are brought into contact with each other just before the adherend is bonded as an adhesive. Specifically, the polymerizable composition and the decomplexing agent are mixed.

There are no particular limitations on the decomplexing agent as long as it has reactivity with the complex. Examples of decomplexing agents are described in, for example, JP 2017-141423 A. Specifically, examples of decomplexing agents include acids, and more specifically, examples of decomplexing agents include polymerizable monomers containing an acidic group, such as (meth)acrylic acid.

The proportion of the polymerizable composition relative to the total amount of the polymerizable kit is, for example, 10% by mass or more, and, for example, 99% by mass or less. The proportion of the decomplexing agent relative to the total amount of the polymerizable kit is, for example, 3% by mass or more, and, for example, 50% by mass or less.

The polymerizable kit can be used in a variety of adhesive applications, particularly those requiring aesthetics and stability. The polymerizable kit can preferably be used as a medical adhesive and/or a dental adhesive.

(Action and Effect)
The polymerizable composition and the polymerizable kit can achieve both good aesthetic appearance and excellent stability.

More specifically, in this polymerizable composition, the alkoxy group-primary amino group-containing compound can effectively suppress the decomposition of the complex in the polymerizable composition during storage, and can maintain the complex extremely stable, thereby suppressing the reaction of the polymerizable monomer. As a result, it is possible to achieve both good aesthetic appearance and excellent stability.

On the other hand, in the case of a polymerizable kit containing this polymerizable composition and a decomplexing agent, when the polymerizable composition comes into contact with the decomplexing agent during use, the primary amine compound is released from the complex, and an organoborane is generated again, which functions as a polymerization initiator to polymerize the polymerizable monomer. This allows for excellent adhesive properties to be exhibited.

(Modification)
Any primary amine compound remaining after the synthesis of the complex can be used as it is as an alkoxy group-primary amino group-containing compound as a stabilizer. In this modification, the primary amine compound is (3) a third primary amine compound that does not contain a secondary amino group but contains an alkoxy group and a primary amino group.

The present invention will be explained below based on examples and comparative examples. However, these examples are merely illustrative to facilitate understanding of the present invention, and the present invention is in no way limited to these. In the following, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass."

In addition, the specific numerical values of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values (numerical values defined as "equal to or less than") or lower limit values (numerical values defined as "equal to or more than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the "Description of the Invention" above.

Example 1
<Synthesis of Complex>
The flask was filled with argon, and 0.2 mol of 3-methoxy-1-propylamine was added to the flask, followed by adding dropwise a solution of 0.1 mol of tri-n-butylborane in tetrahydrofuran to the flask using a dropping funnel.

Specifically, first, while cooling (ice-cooling) the 3-methoxy-1-propylamine in the flask, argon gas was bubbled through the 3-methoxy-1-propylamine, and then a solution of tri-n-butylborane in tetrahydrofuran was added to the flask.

Then, the flask was cooled (on ice) and stirred for 2 hours to remove tetrahydrofuran and obtain a complex. In addition to removing the tetrahydrofuran, the remaining 3-methoxy-1-propylamine was also substantially removed.

<Preparation of polymerizable composition>
41.7 moles of methyl methacrylate (polymerizable monomer), 1 mole of the complex, and 5 moles of 3-methoxy-1-propylamine (stabilizer) were mixed together to prepare a polymerizable composition. The prepared polymerizable composition was filled into a glass sample bottle and sealed.

Example 2 to Comparative Example 3
Polymerizable compositions were obtained in the same manner as in Example 1, except that the formulations shown in Tables 1 to 5 were used. The units corresponding to the numerical values in the formulation columns of Tables 1 to 5 are moles.

[evaluation]
The following items were evaluated, and the results are shown in Tables 1 to 5.

<Stability (thermal stability test)>
Immediately after sealing the polymerizable composition in the sample bottle, 1 mL of the composition was dispensed, and the viscosity V0 was measured using an E-type viscometer (cone-plate type) under conditions of 25° C., 50 rpm, and atmospheric pressure.

Separately, the sample bottle was placed in an oven at 45°C.

After the start of leaving the polymerizable composition, the state of the composition was checked visually and by touch, and when it was determined that the composition had thickened, its viscosity V1 was measured. This was carried out at predetermined intervals.

Then, the number of days of standing was counted until the ratio of viscosity V1 to viscosity V0 (V1/V0) reached 100 or more. The longer this number (the larger the number in the table), the better the stability.

<Aesthetics (color difference)>
Immediately after preparation, 2 mL of the polymerizable composition was placed in a colorless, transparent glass petri dish having a diameter of 30 mm. The polymerizable composition was then set in a spectrophotometer (CM-5/manufactured by KONICA MINOLTA) to measure (L ₀ , a ₀ , b ₀ ).

Next, (L ₁ , a ₁ , b ₁ ) of the polymerizable composition was measured after the number of days when the ratio of viscosity V1 to viscosity V0 (V1/V0) became 100 or more in the stability (thermal stability test).

ΔE was calculated based on the following formula:
ΔE=(L ₁ -L ₀ ) ² +(a ₁ -a ₀ ) ² +(b ₁ -b ₀ ) ²

The color difference of the polymerizable composition was evaluated based on the following evaluation criteria.
A: ΔE was less than 10.
x: ΔE was 10 or more.

Claims (7)

A complex prepared from raw materials including an organoborane and a primary amine compound;
an alkoxy group-primary amino group-containing compound containing an alkoxy group and a primary amino group;
A polymerizable monomer having no acidic group and having a (meth)acryloyl group;
Contains
the polymerizable monomer is at least one selected from the group consisting of an ester of an alkanol having from 1 to 10 carbon atoms and (meth)acrylic acid, an ester of an alcohol containing an oxygen-containing heterocycle and (meth)acrylic acid, tetramethylpiperidinyl (meth)acrylate, a hydroxyalkyl (meth)acrylate, and an ester of a polyhydric alcohol and (meth)acrylic acid;
A dental polymerizable composition, wherein the molar ratio of the primary amino group to 1 molar part of the complex is 2.0 parts by mole or more and 5.0 parts by mole or less. 2. The dental polymerizable composition according to claim 1, wherein the alkoxy group-primary amino group-containing compound is R ^A O-R ^B -NH ₂ (wherein R ^A is an alkyl group having 1 to 6 carbon atoms, and R ^B is an alkylene group having 2 to 9 carbon atoms). 3. The dental polymerizable composition according to claim 1, wherein the alkoxy group has a branched alkyl portion having 3 to 6 carbon atoms. The dental polymerizable composition according to any one of claims 1 to 3, characterized in that the polymerizable monomer is monofunctional. The dental polymerizable composition according to any one of claims 1 to 3, wherein the polymerizable monomer is any one selected from the group consisting of methyl (meth)acrylate, butyl (meth)acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth )acrylate, tetrahydrofurfuryl (meth) acrylate, triethylene glycol di(meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, and (5-ethyl-1,3-dioxane- 5-yl )methyl (meth)acrylate. The dental polymerizable composition according to claim 1 , wherein the primary amine compound further contains an alkoxy group. A dental polymerizable composition according to any one of claims 1 to 6 ,
and a decomplexing agent.