WO2018142846A1

WO2018142846A1 - Polymerizable composition and method for producing polymerizable composition

Info

Publication number: WO2018142846A1
Application number: PCT/JP2018/000145
Authority: WO
Inventors: 大屋　豊尚
Original assignee: 富士フイルム株式会社
Priority date: 2017-01-31
Filing date: 2018-01-09
Publication date: 2018-08-09
Also published as: JPWO2018142846A1; CN110072895A; CN110072895B; JP6679763B2

Abstract

Provided are: a polymerizable composition from which a cured product having high transparency and minimal coloring can be obtained; and a method for producing the polymerizable composition. The polymerizable composition comprises: at least one polyfunctional acrylamide compound selected from the group consisting of a compound represented by general formula (1) and a compound represented by general formula (2); and an alkali metal ion, the content of the alkali metal ion being 0.01 to 2 mass% relative to the total of the content of the polyfunctional acrylamide compound and the content of the alkali metal ion.

Description

Polymerizable composition and method for producing polymerizable composition

The present invention relates to a polymerizable composition and a method for producing the polymerizable composition.

The (meth) acrylamide compound, which is one of the polymerizable compounds, is rich in reactivity, and as a raw material and a crosslinking agent for various polymerizable compositions, industrial materials such as coating materials, paints, printing inks, adhesives, and resist materials. Widely used for industrial purposes. For example, Patent Document 1 discloses an ink composition containing a (meth) acrylamide compound as a radical polymerizable compound.

(Meth) acrylamide compounds are generally produced by reacting (meth) acrylic acid halide, (meth) acrylic anhydride, (meth) acrylic acid ester, and the like with an amine compound ( For example, see Patent Document 2). However, in these methods, particularly when a polyfunctional (meth) acrylamide compound having a plurality of (meth) acrylamide groups in one molecule is produced, the (meth) acrylic group of the obtained (meth) acrylamide compound is added. Further, a side reaction in which the amine compound is added by Michael occurs to produce a by-product. Or the resulting by-product produces a complex impurity that is further amidated. As a result, the yield and purity tend to decrease.

On the other hand, for example, in Patent Document 3, after reacting alkyl alkyl and alkylamine compounds to convert them to aminoamides (amide adducts), the method of thermally decomposing them and the reaction concentration of monoalkylamines are adjusted. A method is disclosed.
However, when producing a polyfunctional (meth) acrylamide compound having a plurality of (meth) acrylamide groups in one molecule, it is necessary to further improve the problem of suppression of by-products.

Further, for example, in Patent Documents 4 and 5, a polyfunctional alkylamine compound and a propionyl halide compound substituted with a halogen atom at the 3-position are reacted in the presence of a base to form an amide compound, and then the presence of a base is present. A production method for obtaining a polyfunctional (meth) acrylamide compound by performing a dehydrohalogenation reaction under is disclosed.

Japanese Patent Laid-Open No. 2005-307198 Japanese Patent Laid-Open No. 4-145055 JP-A-4-208258 JP 2013-194023 A JP2013-194024A

By the way, in recent years, in order to enable application to optical uses and the like, a cured product obtained by curing a polyfunctional (meth) acrylamide compound is required to have excellent transparency and suppression of coloring. ing. However, when a cured product is produced by radical polymerization (photopolymerization or thermal polymerization) using a polyfunctional (meth) acrylamide compound with low purity, the transparency of the cured product may be lowered or coloring may occur. There was something to do. In particular, when it is applied to a cured film for optical use, there is a problem in commercialization.

The present inventor conducted studies to improve the yield and purity of the product polyfunctional (meth) acrylamide compound in the methods for producing polyfunctional (meth) acrylamide compounds described in Patent Documents 2 to 5. As a result, the production methods described in Patent Documents 2 to 5 were able to improve the yield and purity of the polyfunctional (meth) acrylamide compound, but the obtained cured product still has low transparency, or It has been found that coloring may occur. That is, it was confirmed that there is room for further improvement in terms of further improving the transparency of the cured product obtained from the polyfunctional (meth) acrylamide compound and further suppressing the coloring.

Then, this invention makes it a subject to provide the polymeric composition which can give the hardened | cured material with high transparency and suppressed coloring.
Moreover, this invention makes it a subject to provide the manufacturing method of the said polymeric composition.

The present inventor has intensively studied to achieve the above problems. As a result, the present inventors have found that the above problems can be solved by a polymerizable composition containing a polyfunctional (meth) acrylamide compound having a specific structure and a predetermined amount of alkali metal ions, and completed the present invention.
That is, it has been found that the above object can be achieved by the following configuration.

[1] At least one polyfunctional acrylamide compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2):
An alkali metal ion,
A polymerizable composition, wherein the content of the alkali metal ion is 0.01 to 2% by mass relative to the total content of the polyfunctional acrylamide compound and the content of the alkali metal ion.
[2] The content of the alkali metal ion is 0.1 to 1.3% by mass based on the total content of the polyfunctional acrylamide compound and the content of the alkali metal ion. [1] The polymerizable composition described in 1.
[3] The polymerizable composition according to [1] or [2], wherein the alkali metal ion is a sodium ion.
[4] At least one base selected from the group consisting of alkali metal hydroxides, carbonates, and hydrogen carbonates, a compound represented by general formula (3) described later, and a general formula (4 described later) ) And at least one polyfunctional amine compound selected from the group consisting of compounds represented by the following formula: X ¹ CH ₂ CH (R ¹ ) C (═O) X ¹ A first step of obtaining at least one intermediate selected from the group consisting of a compound represented by X) and a compound represented by formula (Y) described later;
A compound represented by the above general formula (1) by reacting at least one base selected from the group consisting of alkali metal hydroxides, carbonates, and hydrogen carbonates with the intermediate, and At least one polyfunctional acrylamide compound selected from the group consisting of the compound represented by the general formula (2) is synthesized, and the compound represented by the general formula (1) and the general formula (2) are represented. A second step of obtaining a crude product containing at least one polyfunctional acrylamide compound selected from the group consisting of compounds and alkali metal ions;
The crude product is purified, and the content of the alkali metal ion is adjusted to 0.01 to 2% by mass with respect to the total content of the polyfunctional acrylamide compound and the content of the alkali metal ion. And a third step of obtaining the polymerizable composition according to [1].
Here, in X ¹ CH ₂ CH (R ¹ ) C (═O) X ¹ , R ¹ represents a hydrogen atom or a methyl group. X ¹ represents a halogen atom. The plurality of X ¹ may be the same as or different from each other.
[5] The method for producing a polymerizable composition according to [4], wherein, in the first step and the second step, the base is a sodium hydroxide, carbonate, or bicarbonate.

ADVANTAGE OF THE INVENTION According to this invention, the polymeric composition which can give the hardened | cured material with high transparency and suppressed coloring can be provided.
Moreover, according to this invention, the manufacturing method of the said polymeric composition can be provided.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Moreover, in the description of group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which contains a substituent with the thing which does not contain a substituent. For example, the “alkyl group” includes not only an alkyl group not containing a substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
In addition, “active light” or “radiation” in the present specification means, for example, deep ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, and electron beams. In this specification, “light” means actinic rays and radiation. Unless otherwise specified, “exposure” in this specification includes not only exposure with far ultraviolet rays, X-rays, EUV, and the like, but also drawing with particle beams such as electron beams and ion beams.
Moreover, in this specification, "(meth) acryl" represents acryl and methacryl. That is, for example, (meth) acrylic acid represents acrylic acid and methacrylic acid, and (meth) acrylic group represents acrylic group and methacrylic group. In the present specification, “(meth) acrylamide” represents acrylamide and methacrylamide.

(Polymerizable composition)
The polymerizable composition of the present invention comprises:
At least one polyfunctional acrylamide compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2);
An alkali metal ion,
The content of the alkali metal ion is 0.01 to 2% by mass with respect to the total content of the polyfunctional acrylamide compound and the content of the alkali metal ion.

By setting it as said structure, the hardened | cured material obtained by hardening | curing the polymeric composition of this invention becomes what has high transparency and coloring was suppressed (henceforth, an effect with high transparency, and / or. The effect of suppressing coloring is also referred to as “the effect of the present invention”).
The mechanism by which the polymerizable composition of the present invention exhibits the above-described effects of the present invention is not necessarily clear, but the mechanism that the present inventors presume will be described below. However, the present invention is not limited to the one in which the effects of the present invention can be obtained by the following mechanism. In other words, even when the effect of the present invention is obtained by a mechanism other than the following mechanism, it is included in the scope of the present invention.

The polymerizable composition containing a polyfunctional acrylamide compound is usually an impurity component (for example, a by-product) such as impurities mixed in from the synthesis raw material stage of the polyfunctional acrylamide compound and impurities produced in the synthesis stage of the polyfunctional acrylamide compound. It is considered that residues such as organic base used in the synthesis and heavy metals are inevitably mixed. The influence of this impurity is conspicuous when the polymerizable composition is concentrated and cured with light irradiation and heating. As a result of this, the cured product is considered to have reduced transparency or coloration.
On the other hand, when the polymerizable composition contains the alkali metal ion in the predetermined amount, the presence state in the cured product of the impurity components inevitably mixed as described above is changed, and the cured product is highly transparent, It is estimated that coloring will be suppressed.
In addition, the present inventor, according to the method for producing a polymerizable composition having the first step to the third step, which will be described later, is a yield of polyfunctional acrylamide compound as compared with the above-described conventional method. In addition, it has been confirmed that the purity is further improved. As a result, the polymerizable composition obtained by the above production method has a high purity of the polyfunctional acrylamide compound contained in the polymerizable composition, that is, the content of impurity components inevitably mixed as described above is further reduced. The Therefore, it is presumed that the effects of the present invention are expressed more preferably in synergy with the above-described effects of the alkali metal ions.
Hereinafter, various components contained in the polymerizable composition of the present invention will be described in detail.

[Polyfunctional acrylamide compounds]
<Compound represented by the general formula (1)>

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. R ¹ is preferably a hydrogen atom. Several R < ¹ > may mutually be same or different, and it is preferable that it is the same.
In the general formula (1), m represents an integer of 2 to 4. The plurality of m may be the same or different from each other, and are preferably the same. The carbon chain represented by C _m H _2m may be a straight chain or a branched chain, and a straight chain is preferable.
In the general formula (1), n represents an integer of 2 to 4. The carbon chain represented by C _n H _2n may be a straight chain or a branched chain, and a straight chain is preferable.
In general formula (1), k represents 0 or 1.

Specific examples of the compound represented by the general formula (1) are shown below, but are not limited thereto.

As the compound represented by the general formula (1), (1) -1, (1) -3, (1) -5 are obtained in that a cured product having higher transparency and coloration is further suppressed can be obtained. Or (1) -7 is preferred, and (1) -1, (1) -3, or (1) -7 is more preferred.

In the general formula (2), R ² represents —CH ₂ CH (R ¹ ) CH ₂ —. A plurality of R ² may be the being the same or different, is preferably identical.
In the general formula (2), R ¹ represents a hydrogen atom or a methyl group. R ¹ is preferably a hydrogen atom. Several R < ¹ > may mutually be same or different, and it is preferable that it is the same.
In the general formula (2), k represents 1.
In general formula (2), m represents 0 or 1. m is preferably 1.
In the general formula (2), n represents an integer of 2 to 6. n is preferably an integer of 2 to 4. Several n may mutually be same or different, and it is preferable that it is the same. The carbon chain represented by C _n H _2n may be a straight chain or a branched chain, and a straight chain is preferable.

Specific examples of the compound represented by the general formula (2) are shown below, but are not limited thereto.

As the compound represented by the general formula (2), (2) -1, (2) -5, or (2)-is preferable in that a cured product having higher transparency and less coloring is obtained. 8 is preferable, and (2) -1 is more preferable.

In the polymerizable composition, the content of the polyfunctional acrylamide compound is not particularly limited, preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total solid content in the polymerizable composition, 10 mass% or more is still more preferable, 20 mass% or more is especially preferable, 99.99 mass% or less is preferable, 99.9 mass% or less is more preferable, 99 mass% or less is still more preferable.
Moreover, it is preferable that a polyfunctional acrylamide compound is contained as a main component in a polymerizable composition especially from a viewpoint excellent in the handleability of a polymerizable composition. Specifically, the content of the polyfunctional acrylamide compound in the polymerizable composition is preferably 90% by mass or more, more preferably 93% by mass or more, and 95% by mass with respect to the total solid content in the polymerizable composition. The above is more preferable, 99.99 mass% or less is preferable, 99.9 mass% or less is more preferable, and 99 mass% or less is still more preferable.

In the polymerizable composition, the polyfunctional acrylamide compound may be a single compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2). More than one species may be used in combination. When two or more polyfunctional acrylamide compounds are used in combination, the total content is preferably within the above range.

[Alkali metal ions]
The polymerizable composition contains an alkali metal ion.
As a kind of alkali metal, lithium, sodium, potassium, rubidium, or cesium is preferable, lithium, sodium, or potassium is more preferable, and sodium is still more preferable.

The alkali metal ion is usually present in the polymerizable composition in the form of a salt with an anion (counter anion). The anion that forms a pair of alkali metal ions can be arbitrarily selected from inorganic or organic anionic species.
Examples of inorganic anions include hydroxide ions, chloride ions, bromide ions, iodide ions, sulfate ions, hydrogen sulfate ions, sulfite ions, carbonate ions, bicarbonate ions, nitrate ions, nitrite ions, phosphorus ions. Acid ions, monohydrogen phosphate ions, dihydrogen phosphate ions, borate ions and the like can be mentioned.
Organic anions include carboxylate ions (for example, formate ion, acetate ion, propionate ion, 3-chloropropionate ion, oxalate ion, benzoate ion, succinate ion, phthalate ion, acrylate ion, And methacrylic acid ions, etc.), sulfonic acid ions (for example, methanesulfonic acid ions, ethanesulfonic acid ions, benzenesulfonic acid ions, p-toluenesulfonic acid ions, alkylbenzenesulfonic acid ions, styrenesulfonic acid ions, and 2-acrylamide- 2-methylpropanesulfonic acid ion, etc.), and phosphonic acid ions (for example, methylphosphonic acid ion, vinylphosphonic acid ion, etc.).
Among them, chloride ion, bromide ion, sulfate ion, or acetate ion is preferable as the anionic species, and chloride ion is more preferable.
In the polymerizable composition, one kind of anion which is a pair of alkali metal ions may be contained alone, or two or more kinds may be contained.

The polymerizable composition has an alkali metal ion content of 0.01 to 2% by mass with respect to the total of the polyfunctional acrylamide compound content and the alkali metal ion content. Hardened | cured material obtained by hardening | curing polymeric composition as content of an alkali metal ion is less than 0.01 mass% with respect to the sum total of content of a polyfunctional acrylamide compound, and content of an alkali metal ion. Is colored. On the other hand, when the content of the alkali metal ion exceeds 2% by mass with respect to the total content of the polyfunctional acrylamide compound and the content of the alkali metal ion, a cured product obtained by curing the polymerizable composition is obtained. Transparency decreases and coloring occurs.
The content of the alkali metal ion is 0.02 to 1.7 mass with respect to the total of the content of the polyfunctional acrylamide compound and the content of the alkali metal ion, in particular, in that the effect of the present invention is more excellent. %, More preferably 0.04 to 1.5% by mass, still more preferably 0.1 to 1.3% by mass, and particularly preferably 0.2 to 1.0% by mass.

In the polymerizable composition, alkali metal ions may be used alone or in combination of two or more. When two or more kinds of alkali metal ions are used in combination, the total content is preferably within the above range.

[Optional ingredients]
The polymerizable composition may contain components other than those described above as optional components.
Examples of optional components include solvents, polymerization initiators, sensitizing dyes, polymerizable monomers (excluding the compounds represented by the above general formula (1) or general formula (2)), fillers, and polymerization inhibitors. , Crosslinking agents, preservatives, antioxidants, ultraviolet absorbers and the like. Any known one can be used arbitrarily.

The form of the polymerizable composition is not particularly limited. The polymerizable composition can take forms such as powder, liquid, paste, pellet, layer, and film.

[Method for producing polymerizable composition]
The manufacturing method of the said polymeric composition is not specifically limited, It can manufacture by arbitrary methods.
The polymerizable composition may be produced by adding the alkali metal ion in a predetermined amount to the polyfunctional acrylamide compound, or is inevitably mixed in the production process of the polyfunctional acrylamide compound (for example, a raw material or You may manufacture by adjusting the alkali metal ion (used as a catalyst etc.) to predetermined amount.
As a method for producing the polymerizable composition, a high-purity polyfunctional acrylamide compound can be synthesized in a high yield, and a polymerizable composition that is superior in transparency and colorability when obtained as a cured product can be obtained. In particular, a production method having the following first to third steps is preferable.

First Step At least one base selected from the group consisting of alkali metal hydroxides, carbonates, and hydrogen carbonates, a compound represented by general formula (3), and a general formula (4) And at least one polyfunctional amine compound selected from the group consisting of the following compounds and X ¹ CH ₂ CH (R ¹ ) C (═O) X ¹ are reacted, and represented by the general formula (X): And a step of obtaining at least one intermediate selected from the group consisting of the compound represented by formula (Y) and the compound represented by formula (Y) (hereinafter simply referred to as “intermediate”).

-2nd process At least 1 type of base chosen from the group which consists of an alkali metal hydroxide, carbonate, and hydrogen carbonate, and the said intermediate body are made to react, and it represents with General formula (1). And at least one polyfunctional acrylamide compound selected from the group consisting of the compound represented by formula (2) and the compound represented by formula (2), and the compound represented by formula (1) and formula (2) A second step of obtaining a crude product containing at least one polyfunctional acrylamide compound selected from the group consisting of compounds and alkali metal ions.

Third step: The crude product is purified, and the content of the alkali metal ion is 0.01 to 2 mass based on the total content of the polyfunctional acrylamide compound and the content of the alkali metal ion. The process of obtaining the said polymeric composition by adjusting to%.

Hereinafter, the first to third steps will be described in detail.
The second step may be carried out after separating and recovering the intermediate synthesized in the first step, or may be carried out continuously without taking out the intermediate synthesized in the first step. Also good. Especially, it is preferable to carry out continuously, without taking out the said intermediate body synthesize | combined in the 1st process at the point which can synthesize | combine a highly purified polyfunctional acrylamide compound with a high yield.

[First step]
Hereinafter, first, various components used in the first step will be described, and then the procedure of the first step will be described in detail.

<Polyfunctional amine compound>
In the first step, at least one polyfunctional amine compound selected from the group consisting of the compound represented by the general formula (3) and the compound represented by the general formula (4) is used as a raw material amine. In addition, the compound represented by General formula (1) is synthesize | combined through the compound represented by General formula (X) by using the compound represented by General formula (3) as a raw material. Moreover, the compound represented by General formula (2) is synthesize | combined through the compound represented by General formula (Y) as an intermediate body, using the compound represented by General formula (4) as a raw material.

In the general formula (3), k, m, and n have the same meanings as k, m, and n in the general formula (1), respectively, and their preferred aspects are also the same. In general formula (3), a plurality of m may be the same as or different from each other.

Specific examples of the compound represented by the general formula (3) are shown below, but are not limited thereto.

The compound represented by the general formula (3) is capable of synthesizing a polyfunctional acrylamide compound with a high purity and a high yield, and has a high degree of transparency and a polymerization property capable of obtaining a cured product in which coloring is further suppressed. From the viewpoint of forming a composition, (3) -1, (3) -2, (3) -3, or (3) -4 is preferred, and (3) -1, (3) -2, or (3 ) -4 is more preferred.

In the general formula (4), k, m, n, and ^{R 2} are each as defined k, m, n, and ^{R 2} and in Formula (2), and its preferred embodiments are also the same. In the general formula (4), a plurality of R ² and n may be the same as or different from each other.

Specific examples of the compound represented by the general formula (4) are shown below, but are not limited thereto.

As the compound represented by the general formula (4), a polyfunctional acrylamide compound can be synthesized with a high purity and a high yield, and a polymerization can be obtained in which a cured product having higher transparency and less coloring can be obtained. (4) -1, (4) -4, or (4) -6 is preferable, and (4) -1 is more preferable, from the viewpoint of forming an adhesive composition.

In addition, as a polyfunctional amine compound, even if it uses individually by 1 type chosen from the group consisting of the compound represented by the compound represented by General formula (3), and General formula (4), it uses 2 or more types together May be.

<Compound Represented by X ¹ CH ₂ CH (R ¹ ) C (═O) X ¹ >
In the compound represented by X ¹ CH ₂ CH (R ¹ ) C (═O) X ¹ , R ¹ represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.
X ¹ represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or a bromine atom, and a chlorine atom. Is more preferable. The plurality of X ¹ may be the same as or different from each other.
As the compound represented by X ¹ CH ₂ CH (R ¹ ) C (═O) X ¹ , 3-chloropropionyl chloride, 3-bromopropionyl chloride, 3-chloropropionyl bromide, or 3-bromopropionyl bromide is preferable. 3-chloropropionyl chloride or 3-bromopropionyl chloride is more preferable, and 3-chloropropionyl chloride is still more preferable.

The amount of the compound represented by X ¹ CH ₂ CH (R ¹ ) C (═O) X ¹ is the total amount of amino groups of the polyfunctional amine compound (when two or more polyfunctional amine compounds are used in combination). Is preferably 1.0 to 2.0 equivalents, more preferably 1.05 to 1.5 equivalents, based on the total amount of amino groups of all polyfunctional amine compounds, More preferably, it is ˜1.3 equivalent.

<Base>
In the first step, at least one base selected from the group consisting of alkali metal hydroxides, carbonates, and bicarbonates is used.
As a kind of alkali metal, lithium, sodium, potassium, rubidium, or cesium is preferable, lithium, sodium, or potassium is more preferable, and sodium is still more preferable.

Examples of the base include lithium hydroxide, lithium carbonate, lithium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, rubidium hydroxide, rubidium carbonate, hydrogen carbonate. Examples include rubidium, cesium hydroxide, cesium carbonate, and cesium bicarbonate.
As the base, lithium hydroxide, lithium carbonate, lithium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, sodium carbonate, or sodium hydrogen carbonate is preferable, potassium hydroxide, potassium carbonate, Potassium hydrogen carbonate, sodium hydroxide, sodium carbonate, or sodium hydrogen carbonate is more preferable, and sodium hydroxide, sodium carbonate, or sodium hydrogen carbonate is still more preferable.

In the first step, the amount of base used is the total amount of amino groups of the polyfunctional amine compound (when two or more polyfunctional amine compounds are used in combination, the total amount of amino groups of all polyfunctional amine compounds). On the other hand, it is preferably 1.0 to 3.0 equivalents, more preferably 1.05 to 2.0 equivalents, and even more preferably 1.1 to 1.6 equivalents.

In the general formula (X), k, m, n and ^{R 1} are each as defined k, m, n, and ^{R 1} and in the general formula (1) and its preferable embodiments are also the same.
X ¹ represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or a bromine atom, and further a chlorine atom. preferable.
In general formula (X), a plurality of R ¹ , X ¹ , and m may be the same as or different from each other.

Specific examples of the compound represented by the general formula (X) are shown below, but are not limited thereto.

As the compound represented by the general formula (X), a cured product cured product in which a polyfunctional acrylamide compound can be synthesized with high purity and high yield, transparency is higher, and coloring is further suppressed is obtained. (X) -1, (X) -3, (X) -5, or (X) -7 is preferred, and (X) -1, (X) -3, Or (X) -7 is more preferred.

In the general formula (Y), k, m, n, ^{R 1,} and ^{R 2} are each as defined k, m, n, ^{R 1} and ^{R 2} in the general formula (2), also same preferred embodiments thereof It is. Further, X ¹ has the same meaning as X ¹ in the general formula (X), also preferred embodiments thereof are also the same. In general formula (Y), a plurality of R ¹ , R ² , X ¹ , and n may be the same as or different from each other.

Specific examples of the compound represented by the general formula (Y) are shown below, but are not limited thereto.

As the compound represented by the general formula (Y), a cured product cured product in which a polyfunctional acrylamide compound can be synthesized with high purity and high yield, transparency is higher, and coloring is further suppressed is obtained. (Y) -1, (Y) -5, or (Y) -8 is preferable, and (Y) -1 is more preferable in that a polymerizable composition can be formed.

<Solvent>
In the reaction for synthesizing the intermediate in the first step, it is preferable to use a solvent. The above reaction may be carried out in a homogeneous system using one type of solvent or two or more compatible solvents, or in a heterogeneous system using two or more types of solvents that are phase-separated.
Examples of the solvent include water, alcohols (for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Ether, polyethylene glycol, etc.), acetonitrile, halogenated alkanes (chloroform, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, etc.), aromatics (benzene, toluene, o-xylene, p-xylene, m-xylene, mesitylene, methoxybenzene, chlorobenzene, o-dichlorobenzene, and nitrobenzene), ketones (acetone, 2-propanone, and 4- Til-2-pentanone), esters (such as methyl acetate, ethyl acetate, and butyl acetate), amides (such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone) , Ethers (such as dimethyl ether, diethyl ether, dibutyl ether, diethylene glycol dimethyl ether, dioxane, and tetrahydrofuran), dimethyl sulfoxide, and sulfolane.
Among them, water, alcohols (eg, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol), acetonitrile, ketones (acetone, 2-propanone, 4-methyl-2-pentanone, etc.) , Esters (such as methyl acetate, ethyl acetate, and butyl acetate) or amides (such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone) are preferable, and water, alcohol (Eg, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, etc.), acetonitrile, or ketones (acetone, 2-propanone, etc.) are more preferred.
In the first step, the reaction is preferably performed in a two-phase system of water and an organic solvent other than water.

In the first step, the concentration of the polyfunctional amine compound in the reaction solution is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, with respect to the total mass of the reaction solution. More preferred is mass%.
In the first step, the reaction temperature is preferably −10 to 40 ° C., more preferably 0 to 30 ° C., and further preferably 5 to 25 ° C.
In the first step, the reaction time is preferably 30 minutes or longer. The upper limit of the reaction time varies depending on the scale of the reaction in order to control it within the above-mentioned preferable reaction temperature since this step is an exothermic reaction, but is preferably 24 hours or less, preferably 12 hours or less. More preferably, it is more preferably 6 hours or less.
In the first step, the product intermediate can be separated and recovered from the reaction product solution by a conventional method. For example, it can be recovered by an extraction operation using an organic solvent, crystallization using a poor solvent, column chromatography using silica gel, or the like. Moreover, you may perform a 2nd process continuously, without isolate | separating and collect | recovering from a reaction system.

[Second step]
Hereinafter, first, various components used in the second step will be described, and then the step of the second step will be described in detail.

The intermediate used in the second step is the intermediate obtained in the first step.

Moreover, the base used at the 2nd process is synonymous with the base used at the 1st process mentioned above, The preferable aspect is also the same. In addition, as a base used at a 2nd process, it is preferable to use the hydroxide of an alkali metal especially at the point of improving the yield of polyfunctional acrylamide more.
In the second step, the amount of base used is the total amount of the group represented by X ¹ CH ₂ CH (R ¹ ) C (═O) of the above intermediate (when two or more intermediates are used in combination) The total amount of groups represented by X ¹ CH ₂ CH (R ¹ ) C (═O) in all intermediates is preferably 1.0 to 5.0 equivalents, 1.1 to 4.0 equivalents are more preferable, and 1.2 to 3.0 equivalents are even more preferable.
In addition, the base used in a 1st process and a 2nd process may be the same, or may differ.

In the reaction for synthesizing the polyfunctional acrylamide compound in the second step, it is preferable to use a solvent. The above reaction may be carried out in a homogeneous system using one type of solvent or two or more compatible solvents, or in a heterogeneous system using two or more types of solvents that are phase-separated.
The solvent that can be used in the second step is the same as the solvent mentioned in the first step described above, and its preferred embodiment is also the same. In the second step, the reaction is preferably performed in a two-layer system of water and an organic solvent other than water.

In the second step, the concentration of the intermediate in the reaction solution is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass with respect to the total mass of the reaction solution. Is more preferable.
In the second step, the reaction temperature is preferably −5 to 60 ° C., more preferably 0 to 50 ° C., and further preferably 10 to 40 ° C.
In the second step, the reaction time is preferably 30 minutes or longer. Regarding the upper limit of the reaction time, since this step is an exothermic reaction, it varies depending on the scale of the reaction in order to control it within the above-mentioned preferable reaction temperature, but it is preferably 24 hours or less, preferably 18 hours or less. More preferably, it is more preferably 12 hours or less.
In the second step, the product polyfunctional acrylamide compound can be separated and recovered from the reaction product solution by a conventional method. For example, it can be recovered by an extraction operation using an organic solvent, crystallization using a poor solvent, column chromatography using silica gel, or the like.

[Third step]
The crude product obtained through the second step contains a predetermined amount or more of alkali metal ions derived from the base used in the first step and the second step. For this reason, the process of refine | purifying the said crude product and adjusting the content of the said alkali metal ion as a 3rd process is implemented. In addition, the crude product here means the reaction product liquid which passed through the 2nd process, for example.
The purification method is not particularly limited. For example, a method of transferring an alkali metal ion component to an aqueous phase by adding water to a crude product to prepare a two-phase system of an organic phase and an aqueous phase and stirring the mixture. Add the crude product to a solvent with low solubility of alkali metal ion component (for example, acetone, ethyl methyl ketone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, 1-propanol, 2-propanol, butanol, etc.) After removing the alkali metal ion component by filtration, removing the alkali metal ion component with an ion exchange resin, removing the alkali metal ion component with an ultrafiltration membrane, or silica gel chromatography. For chromatography, gel filtration chromatography, or ion exchange chromatography A method in which the removal of alkali metal ion component Ri and the like. By the said refinement | purification, the alkali metal ion in a crude product can be adjusted to predetermined amount, and the said polymeric composition which has a polyfunctional acrylamide compound and predetermined amount of alkali metal ion can be manufactured.

In addition, as a manufacturing method of a polyfunctional acrylamide compound, the following general manufacturing method using an amine compound as a starting material other than the method of manufacturing through the 1st process and 2nd process mentioned above, for example is mentioned.
Production method 1 A method of reacting an amine compound and an acid halide compound.
-Manufacturing method 2 The method of making an amine compound and an acid anhydride react.
Production method 3 A method in which an amine compound and a carboxylic acid compound are reacted in the presence of a condensing agent.
Production method 4 A method of synthesizing a polyfunctional acrylamide compound from an amine compound and an ester compound by an ester amide exchange reaction.

These reactions can be carried out with reference to the methods described in New Experimental Chemistry Course 14 Synthesis of organic compounds and Reaction (V) Protection of 11.6 amino groups P.2555 to P.2569.

However, in the method for producing the polyfunctional acrylamide compound listed above, a complicated by-product is often generated, and this by-product may cause coloration of the cured product or decrease in transparency.
On the other hand, according to the method for producing a polymerizable composition through the first step to the third step described above, the content of complex by-products often generated in the above-described general production method is remarkably suppressed. A polyfunctional acrylamide compound having a high purity can be obtained in a high yield.
The preferable purity of the polyfunctional acrylamide compound obtained through the third step (the purity of the organic component by HPLC (high performance liquid chromatography) method detected by UV (ultraviolet) absorption) is preferably 90% or more, and 93% or more. Is more preferable, and 95% or more is still more preferable.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the following examples.
In addition, the number attached | subjected to the polyfunctional acrylamide compound and raw material amine which are explained in full detail behind intends the number of the exemplary compound of the polyfunctional acrylamide compound and raw material amine mentioned above.

[Example 1]
[Synthesis of polyfunctional acrylamide compound (compound (1) -1)]
<Synthesis of Exemplary Compound (1) -1>
(First step)
In a 1 L three-necked flask equipped with a stirrer, diethylenetriamine ((3) -1 exemplified above) (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.3 g, sodium hydroxide 16.8 g (1. 4 equivalents), 56 g of acetonitrile, and 67 g of water were taken, and the reaction solution in the flask was stirred in an ice bath until the sodium hydroxide was completely dissolved. To the above three-necked flask, 45.7 g of 3-chloropropionic acid chloride (1.2 equivalents relative to the total of amino groups) was added dropwise over 2 hours while controlling the internal temperature to be 15 ° C. or lower. Stir for 15 minutes. The disappearance of the raw material was confirmed by ¹ H-NMR (nuclear magnetic resonance). The lower phase of the reaction solution was removed to obtain a solution of intermediate (X) -1. The obtained solution was directly used in the next step without separating and recovering intermediate (X) -1.
(Second step)
The solution of intermediate (X) -1 obtained in the previous step was placed in a 1 L three-necked flask equipped with a stirrer. Separately, a solution in which 26.4 g of sodium hydroxide (2.2 equivalents based on the total amount of 3-chloropropionyl group of intermediate (X) -1) was dissolved in 106 g of water was prepared, and this solution was added to the above three-neck flask. The solution was added dropwise over 30 minutes while controlling the internal temperature to be 20 ° C. or lower, and further stirred for 2 hours. The disappearance of the raw material was confirmed by ¹ H-NMR. Next, concentrated hydrochloric acid was further added to the flask to neutralize excess sodium hydroxide.
(Third step)
The lower layer of the reaction solution was removed, and the upper layer (organic layer) was concentrated under reduced pressure. The component containing alkali metal ions gradually precipitated by concentration under reduced pressure. By adjusting the concentration by measuring the amount of alkali metal ions remaining in the solution portion, the amount of alkali metal ions remaining was adjusted to be the alkali metal ion content of Example 1 in Table 1. The components containing precipitated alkali metal ions were removed by celite filtration. A product containing Exemplified Compound (1) -1 is obtained by adding 2-butanone as a poor solvent to the resulting solution, performing crystallization at a liquid temperature of −5 ° C., and filtering and drying the precipitated crystals. 22 g was obtained. The yield and HPLC purity of the obtained exemplary compound (1) -1 in the product are shown in Table 1. The product contained Exemplary Compound (1) -1 and sodium ion.
The product produced by the above production method corresponds to the polymerizable composition A1 containing a polyfunctional acrylamide compound (compound (1) -1) and an alkali metal ion.

[Examples 4 to 7, 13, 14]
[Synthesis of polyfunctional acrylamide compound (compound (1) -1)]
Compound (1) -1 was synthesized in the same manner as in Example 1 except that the type of base used in the first step and / or the second step of Example 1 was changed as shown in Table 1. In addition, the same molar amount as Example 1 was used for the addition amount of the base. The yield and HPLC purity of Exemplified Compound (1) -1 in the products obtained in Examples 4 to 7, 13, and 14 are shown in Table 1.
The products produced by the above production method correspond to polymerizable compositions A4 to A7, A13, and A14 each containing a polyfunctional acrylamide compound (compound (1) -1) and alkali metal ions.

[Example 2]
[Synthesis of polyfunctional acrylamide compound (compound (1) -1)]
Compound (1) -1 was synthesized in the same manner as in Example 1, except that the third step of Example 1 was changed as follows.
The lower layer of the reaction solution after the reaction in the second step was removed, and the upper layer (organic layer) was concentrated under reduced pressure. The component containing alkali metal ions gradually precipitated by concentration under reduced pressure. By adjusting the concentration by measuring the amount of alkali metal ions remaining in the solution portion, the alkali metal ions to be remained were adjusted to have the alkali metal ion content of Example 2 in Table 1. The components containing precipitated alkali metal ions were removed by celite filtration. To the obtained solution, 2-butanone was added as a poor solvent, and crystallization was performed at a liquid temperature of −5 ° C., and the precipitated crystals were collected by filtration and dried.
The yield and HPLC purity of Exemplified Compound (1) -1 in the product obtained in Example 2 are shown in Table 1.
The product produced by the above production method corresponds to the polymerizable composition A2 containing a polyfunctional acrylamide compound (compound (1) -1) and an alkali metal ion.

Example 3
[Synthesis of polyfunctional acrylamide compound (compound (1) -1)]
Compound (1) -1 was synthesized in the same manner as in Example 1, except that the third step of Example 1 was changed as follows.
The lower layer of the reaction solution after the reaction in the second step was removed, and the upper layer (organic layer) was concentrated under reduced pressure. The component containing alkali metal ions gradually precipitated by concentration under reduced pressure. By adjusting the concentration by measuring the amount of alkali metal ions remaining in the solution portion, the alkali metal ions to be remained were adjusted to have the alkali metal ion content of Example 3 in Table 1. The components containing precipitated alkali metal ions were removed by celite filtration. To the obtained solution, 2-butanone was added as a poor solvent, and crystallization was performed at a liquid temperature of −5 ° C., and the precipitated crystals were collected by filtration and dried.
The yield and HPLC purity of Exemplified Compound (1) -1 in the product obtained in Example 3 are shown in Table 1.
The product produced by the above production method corresponds to the polymerizable composition A3 containing a polyfunctional acrylamide compound (compound (1) -1) and an alkali metal ion.

Example 8
[Synthesis of polyfunctional acrylamide compound (compound (1) -3)]
Compound (1) -3 was synthesized in the same manner as in Example 1 except that the type of polyfunctional amine in Example 1 was changed to (3) -2. The polyfunctional amine was used in the same molar amount as in Example 1. The yield and HPLC purity of Exemplary Compound (1) -3 in the product obtained in Example 8 are shown in Table 1.
The product produced by the above production method corresponds to the polymerizable composition A8 containing a polyfunctional acrylamide compound (compound (1) -3) and an alkali metal ion.

Example 9
[Synthesis of polyfunctional acrylamide compound (compound (1) -7)]
Compound (1) -7 was synthesized in the same manner as in Example 1 except that the type of polyfunctional amine in Example 1 was changed to (3) -4. The polyfunctional amine was used in the same molar amount as in Example 1. The yield and HPLC purity of Exemplified Compound (1) -7 in the product obtained in Example 9 are shown in Table 1.
The product produced by the above production method corresponds to the polymerizable composition A9 containing a polyfunctional acrylamide compound (compound (1) -7) and an alkali metal ion.

Example 10
[Synthesis of polyfunctional acrylamide compound (compound (2) -1)]
Compound (2) -1 was synthesized in the same manner as in Example 1, except that the type of polyfunctional amine in Example 1 was changed to (4) -1. The polyfunctional amine was used in the same molar amount as in Example 1. The yield and HPLC purity of Exemplified Compound (2) -1 obtained in Example 10 are shown in Table 1.
The product produced by the above production method corresponds to the polymerizable composition A10 containing a polyfunctional acrylamide compound (compound (2) -1) and an alkali metal ion.

Example 11
[Synthesis of polyfunctional acrylamide compound (compound (1) -1)]
Compound (1) -1 was synthesized in the same manner as in Example 1, except that the third step of Example 1 was changed as follows.
The lower phase of the reaction solution after the reaction in the second step was removed and concentrated under reduced pressure. The operation of adding acetonitrile and concentrating under reduced pressure was repeated 5 times to reduce the water in the solvent by azeotropic distillation. The precipitated inorganic component was removed by celite filtration to adjust the amount of alkali metal ions. To the resulting solution, 2-butanone was added as a poor solvent and crystallized at a liquid temperature of 5 ° C., and the precipitated crystals were collected by filtration and dried.
The yield and HPLC purity of Exemplified Compound (1) -1 in the product obtained in Example 11 are shown in Table 1.
The product produced by the above production method corresponds to the polymerizable composition A11 containing a polyfunctional acrylamide compound (compound (1) -1) and an alkali metal ion.

Example 12
[Synthesis of polyfunctional acrylamide compound (compound (1) -1)]
Compound (1) -1 was synthesized in the same manner as in Example 1, except that the third step of Example 1 was changed as follows.
The lower phase of the reaction solution after the reaction in the second step was removed and concentrated under reduced pressure. The precipitated inorganic component was removed by celite filtration to adjust the amount of alkali metal ions. To the resulting solution, 2-butanone was added as a poor solvent and crystallized at a liquid temperature of −5 ° C., and the precipitated crystals were collected by filtration and dried.
The yield and HPLC purity of exemplary compound (1) -1 in the product obtained in Example 12 are shown in Table 1.
The product produced by the above production method corresponds to the polymerizable composition A12 containing a polyfunctional acrylamide compound (compound (1) -1) and an alkali metal ion.

[Comparative Example 1]
[Synthesis of polyfunctional acrylamide compound (compound (1) -1)]
Compound (1) -1 was synthesized in the same manner as in Example 1, except that the third step of Example 1 was changed as follows.
The upper phase solution obtained by removing the lower phase of the reaction solution after the reaction in the second step was subjected to strong acid cation exchange resin IR124 and strongly basic anion exchange resin IRA400J (both manufactured by Dow Chemical Co.). Desalting was performed by sequential treatment. Thereafter, the obtained solution was concentrated under reduced pressure. To the obtained main liquid, 2-butanone is added as a poor solvent, crystallized at a liquid temperature of 5 ° C., and the precipitated crystals are collected by filtration and dried to obtain a product containing exemplary compound (1) -1 Got.
The yield and HPLC purity of Exemplified Compound (1) -1 in the product obtained in Comparative Example 1 are shown in Table 1.
The product produced by the above production method corresponds to the comparative polymerizable composition A1 containing a polyfunctional acrylamide compound (compound (1) -1) and an alkali metal ion.

[Comparative Example 2]
[Synthesis of polyfunctional acrylamide compound (compound (1) -1)]
Compound (1) -1 was synthesized in the same manner as in Example 1, except that the third step of Example 1 was changed as follows.
After removing the lower phase of the reaction solution after the reaction in the second step and concentrating under reduced pressure, the precipitated inorganic component was removed by Celite filtration to adjust the amount of alkali metal ions. 2-butanone as a poor solvent is added to the obtained main liquid, crystallization is performed at a liquid temperature of −10 ° C., and the precipitated crystals are collected by filtration and dried to produce a compound containing exemplary compound (1) -1. I got a thing.
The yield and HPLC purity of Exemplified Compound (1) -1 in the product obtained in Comparative Example 2 are shown in Table 1.
The product produced by the above production method corresponds to the comparative polymerizable composition A2 containing a polyfunctional acrylamide compound (compound (1) -1) and an alkali metal ion.

[Comparative Examples 3 and 4]
[Synthesis of polyfunctional acrylamide compound (compound (1) -1)]
Compound (1) -1 was synthesized in the same manner as in Example 1 except that the type of base in Example 1 was changed to triethylamine as shown in Table 1. In addition, the same molar amount as Example 1 was used for the addition amount of the base. The yield and HPLC purity of Exemplified Compound (1) -1 in the products obtained in Comparative Examples 3 and 4 are shown in Table 1.
In addition, the product manufactured in Comparative Example 3 corresponds to the comparative polymerizable composition A3. In the comparative polymerizable composition A3 of Comparative Example 3, the concentration of alkali metal ions was below the detection limit.
The product produced in Comparative Example 4 corresponds to the comparative polymerizable composition A4 containing a polyfunctional acrylamide compound (compound (1) -1) and an alkali metal ion.

[Comparative Example 5]
[Synthesis of polyfunctional acrylamide compound (compound (1) -1)]
Compound (1) -1 was synthesized by reacting diethylenetriamine and acrylic acid chloride in the same manner as in the synthesis example of polyfunctional acrylamide described in Example 1 of JP-A-4-145055. The yield and HPLC purity of Exemplified Compound (1) -1 in the product obtained in Comparative Example 5 are shown in Table 1.
The product produced by the above production method corresponds to the comparative polymerizable composition A5 containing a polyfunctional acrylamide compound (compound (1) -1) and an alkali metal ion.

[Measurement of purity (HPLC purity)]
The purity of the polyfunctional acrylamide compound in the products obtained in Examples 1 to 14 and Comparative Examples 1 to 5 was measured by the HPLC method as follows.
Column: Shiseido CAPCELLPAK C18MGII 5 μm 4.6 × 250 mm
Mobile phase: A / B = 70/30 (capacity ratio)
A liquid: 10 mM ammonium acetate aqueous solution B liquid: 10 mM ammonium acetate methanol solution Flow rate: 1.0 mL / min.
Column temperature: 40 ° C
Detection: UV (210 nm)
Injection volume: 10 μL

[Measurement of content of alkali metal ions]
The content of alkali metal ions in the products obtained in Examples 1 to 14 and Comparative Examples 1 to 5 was measured by ion chromatography as follows. In addition, content of an alkali metal ion is corresponded to the value computed as a ratio with respect to the sum total of content of a polyfunctional acrylamide compound, and content of an alkali metal ion.
Apparatus: DX-320 ion chromatography analyzer manufactured by DIONEX Column: Ionpac CS12A 4 × 250 mm manufactured by DIONEX
Mobile phase: 20 mM methanesulfonic acid aqueous solution Flow rate: 1.0 mL / min.
Column temperature: 35 ° C
Injection volume: 10 μL

[Evaluation of cured product]
(Preparation of the cured product of Example 1)
Polymeric composition B1 was produced by adding 3 parts by mass of Irgacure 2959 (manufactured by BASF) as a photopolymerization initiator and 400 parts by mass of methanol as a solvent to 97 parts by mass of the polymerizable composition A1 obtained in Example 1.
A coating layer was formed by coating the polymerizable composition B1 on a PET film (polyethylene terephthalate, product name “A4300”, manufactured by Toyobo Co., Ltd.) using a bar coater so that the dry film thickness was 5 μm. . Next, the PET film with a coating layer was placed in a drying oven at 50 ° C. and dried for 5 minutes. Next, using an “ECS-401G (trade name)” UV (ultraviolet) exposure machine (the light source is a high-pressure mercury lamp) manufactured by Eye Graphic Co., Ltd., an exposure amount of 4 J / cm ² (irradiation time is 5 seconds) The dried coating layer was cured by exposure (ultraviolet irradiation) to obtain a cured product (cured film).

(Production of cured products of Examples 2 to 14 and Comparative Examples 1 to 5)
Further, in the production of the cured product of Example 1, 97 parts by mass of the polymerizable composition A1 obtained in Example 1 was used for each polymerizable composition obtained in Examples 2 to 14 or Comparative Examples 1 to 5. (Polymerizable compositions A2 to A14 or comparative polymerizable compositions A1 to A5) Polymerizable compositions B2 to B14 and comparative polymerizable compositions B1 to B5 were prepared in the same manner except that the amount was 97 parts by mass. The cured product (cured film) was obtained by the same method as in Example 1.

About the obtained hardened | cured material, the transparency and coloring property were measured with the following evaluation method.

[Evaluation of transparency]
The light transmittance at 800 nm was measured by the method described in JIS K 7361-1: 1997, and the transparency was evaluated (unit:%). A higher light transmittance means better transparency. The evaluation of transparency is preferably 87% or more, more preferably 88% or more, and still more preferably 90% or more.

[Evaluation of coloring properties]
The light transmittance at 400 nm was measured by the method described in JIS K 7361-1: 1997 to evaluate the coloring. Higher light transmittance means smaller coloration. The evaluation of coloring is preferably 85% or more, more preferably 87% or more, and still more preferably 88% or more.

Table 1 shows the following.
First, the transparency and coloring of the cured product obtained by curing the polymerizable composition will be described.
From a comparison between Examples 1 to 14 and Comparative Examples 1 to 5, the content of alkali metal ions in the polymerizable composition was based on the sum of the content of the polyfunctional acrylamide compound and the content of alkali metal ions. When the content is 0.01 to 2% by mass, it can be seen that the obtained cured product has high transparency and small coloring.
In particular, from the comparison between Examples 1 to 14 and Comparative Example 1, the content of alkali metal ions in the polymerizable composition is based on the sum of the content of polyfunctional acrylamide compound and the content of alkali metal ions. When it is less than 0.01% by mass, it can be confirmed that coloring of the cured product tends to increase. Further, from the comparison between Examples 1 to 14 and Comparative Example 2, the content of the alkali metal ion in the polymerizable composition is based on the sum of the content of the polyfunctional acrylamide compound and the content of the alkali metal ion. In the case of more than 2% by mass, it can be confirmed that the transparency of the cured product is lowered and the coloring is also increased.
Further, from the comparison between Examples 1 to 14 and Comparative Examples 3 to 5, when manufactured by a method different from the manufacturing method of the polymerizable composition having the first to third steps (Comparative Examples 3 to 5) Was confirmed to have a low yield and low purity of the polyfunctional acrylamide compound. In Comparative Examples 3 to 5, it was confirmed that coloring of the cured product was increased due to the low content of alkali metal ions and the low purity of the polyfunctional acrylamide compound. On the other hand, according to the method for producing a polymerizable composition having the first to third steps, the polyfunctional acrylamide compound can be obtained in high yield and high purity, and the cured product has high transparency, and It was confirmed that coloring was small.
Further, from the comparison of Examples 1 to 7, 11, and 12, the content of alkali metal ions is 0.1 to 1 with respect to the sum of the content of polyfunctional acrylamide compound and the content of alkali metal ions. When it is 3 mass%, it turns out that the hardened | cured material obtained is more transparent and coloring is smaller.
Further, from the comparison of Examples 1 to 7, 13, and 14, it can be seen that when the alkali metal ion species is sodium ion, the obtained cured product is more transparent and less colored.

Next, the purity and yield of the polyfunctional acrylamide compound in the product obtained by the method for producing a polymerizable composition having the first to third steps will be described.
From comparison between Examples 1 to 14 and Comparative Examples 3 to 5, it can be seen that the method for producing a polymerizable composition having the first to third steps can synthesize a polyfunctional acrylamide compound with high purity and high yield. .
Further, from the comparison between Example 1 and Examples 13 and 14, when sodium is used as the alkali metal in the alkali metal hydroxide, carbonate, or bicarbonate used as the base, lithium and Compared with the case of using potassium, it is excellent in that the reaction proceeds at a high yield.
From the comparison of Examples 1 to 7, the base used in the first step is not greatly different in yield regardless of whether it is a hydroxide, carbonate, or bicarbonate, but it is used in the second step. It can be seen that it is preferable to use a hydroxide as the base in terms of yield.
From the comparison of Examples 1, 8, 9, and 10, it can be seen that the production method of the present invention can synthesize a polyfunctional acrylamide compound with high purity and high yield regardless of the kind of the raw material polyfunctional amine compound.
From the above, the effects of the present invention are clear.

Claims

At least one polyfunctional acrylamide compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2);
An alkali metal ion,
A polymerizable composition, wherein the content of the alkali metal ion is 0.01 to 2% by mass relative to the total content of the polyfunctional acrylamide compound and the content of the alkali metal ion.

In general formula (1), R 1 represents a hydrogen atom or a methyl group. m represents an integer of 2 to 4. n represents an integer of 2 to 4. k represents 0 or 1; The plurality of R 1 and m may be the same or different from each other.

In the general formula (2), R 2 represents —CH 2 CH (R 1 ) CH 2 —. R 1 represents a hydrogen atom or a methyl group. k represents 1. m represents 0 or 1; n represents an integer of 2 to 6. The plurality of R 1 , R 2 , and n may be the same as or different from each other.
The content of the alkali metal ion is 0.1 to 1.3% by mass with respect to the total content of the polyfunctional acrylamide compound and the content of the alkali metal ion. Polymerizable composition.
The polymerizable composition according to claim 1 or 2, wherein the alkali metal ion is a sodium ion.
From at least one base selected from the group consisting of alkali metal hydroxides, carbonates and bicarbonates, compounds represented by general formula (3) and compounds represented by general formula (4) At least one polyfunctional amine compound selected from the group consisting of X 1 CH 2 CH (R 1 ) C (═O) X 1 and a compound represented by the general formula (X) A first step of obtaining at least one intermediate selected from the group consisting of compounds represented by formula (Y);
A compound represented by the general formula (1) by reacting at least one base selected from the group consisting of alkali metal hydroxides, carbonates, and hydrogen carbonates with the intermediate; The compound represented by the general formula (1) and the general formula (2) are synthesized by synthesizing at least one polyfunctional acrylamide compound selected from the group consisting of the compounds represented by the general formula (2). A second step of obtaining a crude product containing at least one polyfunctional acrylamide compound selected from the group consisting of compounds and alkali metal ions;
The crude product is purified, and the content of the alkali metal ion is adjusted to 0.01 to 2% by mass with respect to the total content of the polyfunctional acrylamide compound and the content of the alkali metal ion. And a third step of obtaining the polymerizable composition according to claim 1.
Here, in X 1 CH 2 CH (R 1 ) C (═O) X 1 , R 1 represents a hydrogen atom or a methyl group. X 1 represents a halogen atom. The plurality of X 1 may be the same as or different from each other.

In general formula (3), m represents an integer of 2 to 4. n represents an integer of 2 to 4. k represents 0 or 1; A plurality of m may be the same as or different from each other.

In the general formula (4), R 2 represents —CH 2 CH (R 1 ) CH 2 —. R 1 represents a hydrogen atom or a methyl group. k represents 1. m represents 0 or 1; n represents an integer of 2 to 6. The plurality of R 2 and n may be the same or different from each other.

In general formula (X), R 1 represents a hydrogen atom or a methyl group. X 1 represents a halogen atom. m represents an integer of 2 to 4. n represents an integer of 2 to 4. k represents 0 or 1; The plurality of R 1 , X 1 , and m may be the same or different from each other.

In general formula (Y), R 2 represents —CH 2 CH (R 1 ) CH 2 —. R 1 represents a hydrogen atom or a methyl group. X 1 represents a halogen atom. k represents 1. m represents 0 or 1; n represents an integer of 2 to 6. A plurality of R 1 , R 2 , X 1 , and n may be the same as or different from each other.
The method for producing a polymerizable composition according to claim 4, wherein, in the first step and the second step, the base is sodium hydroxide, carbonate, or bicarbonate.