JP2022122074A - Thiourethane (meth)acrylate composition, monomer composition, curable composition, molded body, and method for producing thiourethane (meth)acrylate composition - Google Patents

Abstract

To provide a thiourethane (meth)acrylate composition that has excellent bending strength in the case of a cured product and reduced polymerization shrinkage rate.SOLUTION: A thiourethane (meth)acrylate composition contains a thiourethane (meth)acrylate monomer (D) which is a reaction product of a thiol compound (A) including two or more mercapto groups, an iso(thio)cyanate compound (B) including two or more iso(thio)cyanate groups, and a hydroxy (meth)acrylate compound (C) being a (meth)acrylate compound including a hydroxy group, where a molar ratio [a/b] being a ratio of a mole number a of a mercapto group in the thiol compound (A) with respect to a mole number b of the iso(thio)cyanate group in the iso(thio)cyanate compound (B) is more than 0.20 and 0.50 or less.SELECTED DRAWING: None

Description

The present disclosure relates to thiourethane (meth)acrylate compositions, monomer compositions, curable compositions, moldings, and methods of making thiourethane (meth)acrylate compositions.

(Meth)acrylate compounds are widely used as monomers in curable compositions.
For example, Patent Document 1 discloses (meth)acrylate (D) as a monomer capable of giving a cured product having both high toughness and rigidity. The (meth)acrylate (D) in the same document includes a thiol compound (A) having two or more mercapto groups, an iso(thio)cyanate compound (B) having two or more iso(thio)cyanate groups, and a polymerizable It is a reaction product with a hydroxy (meth)acrylate compound (C) having one or more groups. The same document also discloses a composition containing a (meth)acrylate (D).

WO2019/107323

However, for a composition containing a (meth)acrylate compound used as a monomer (hereinafter also referred to as a (meth)acrylate monomer), the polymerization shrinkage rate is reduced from the viewpoint of the dimensional accuracy of the molded product that is the cured product of the composition. (ie, to reduce volume shrinkage during polymerization). On the other hand, when the polymerization shrinkage rate of the composition is reduced, the bending strength of the cured product obtained by curing the composition may be insufficient.
An object of one aspect of the present disclosure is a thiourethane (meth)acrylate composition, a monomer composition, a curable composition, and the curable composition, which are excellent in bending strength of a cured product and have a reduced polymerization shrinkage rate. It is an object of the present invention to provide a molded article which is a cured product of a product, and a method for producing a thiourethane (meth)acrylate composition capable of producing the above thiourethane (meth)acrylate composition.

Means for solving the above problems include the following aspects.
<1> A thiol compound (A) containing two or more mercapto groups, an iso(thio)cyanate compound (B) containing two or more iso(thio)cyanate groups, and a (meth)acrylate compound containing a hydroxy group. A thiourethane (meth)acrylate composition containing a hydroxy (meth)acrylate compound (C) and a thiourethane (meth)acrylate monomer (D) which is a reaction product of
The molar ratio [SH/NCO], which is the ratio of the number of moles of mercapto groups in the thiol compound (A) to the number of moles of the iso(thio)cyanate groups in the iso(thio)cyanate compound (B), is 0. is more than 20 and 0.50 or less,
A thiourethane (meth)acrylate composition.
<2> A thiol compound (A) that is a compound containing two or more mercapto groups, an iso(thio)cyanate compound (B) that is a compound containing two or more iso(thio)cyanate groups, and a hydroxy group ( containing a hydroxy (meth)acrylate compound (C) which is a meth)acrylate compound and a thiourethane (meth)acrylate monomer (D) which is a reaction product of
The polymerization shrinkage rate is 6.0% or less,
A thiourethane (meth)acrylate composition.
<3> The thiourethane (meth)acrylate composition according to <1> or <2>, wherein the thiol compound (A) has three or four mercapto groups.
<4> The thiourethane (meth)acrylate composition according to any one of <1> to <3>, wherein the iso(thio)cyanate compound (B) contains an aromatic ring.
<5> The thiourethane (meth)acrylate composition according to any one of <1> to <4>,
a monomer other than the thiourethane (meth)acrylate monomer (D);
A monomer composition containing
<6> A monomer other than the thiourethane (meth)acrylate monomer (D) is a (meth)acrylate monomer (E) that is a (meth)acrylate monomer other than the thiourethane (meth)acrylate monomer (D).
The monomer composition according to <5>.
<7> The monomer composition according to <5> or <6>, wherein the content of the thiourethane (meth)acrylate monomer (D) is more than 0% by mass and 10% by mass or less with respect to the total amount of the monomer composition. thing.
<8> Monomers other than the thiourethane (meth)acrylate monomer (D) include a (meth)acrylate monomer (E1) containing a urethane bond and two or more (meth)acryloyl groups, and the (meth)acrylate monomer ( A (meth)acrylate monomer (E2) that is a (meth)acrylate monomer other than E1),
The number of mercapto groups in the thiol compound (A) is 3 or 4,
The content of the thiourethane (meth)acrylate monomer (D) is more than 0% by mass and 10% by mass or less with respect to the total amount of the monomer composition.
The monomer composition according to any one of <5> to <7>.
<9> Curing containing the thiourethane (meth)acrylate composition according to any one of <1> to <4> or the monomer composition according to any one of <5> to <8> sex composition.
<10> The curable composition according to <9>, further comprising a polymerization initiator.
<11> The curable composition according to <9> or <10>, which is a composition for dental materials.
<12> A molded article which is a cured product of the curable composition according to any one of <9> to <11>.
<13> A thiol compound (A) containing two or more mercapto groups, an iso(thio)cyanate compound (B) containing two or more iso(thio)cyanate groups, and a (meth)acrylate compound containing a hydroxy group. A method for producing a thiourethane (meth)acrylate composition containing a hydroxy (meth)acrylate compound (C) and a thiourethane (meth)acrylate monomer (D) which is a reaction product of
a reaction step of reacting the thiol compound (A), the iso(thio)cyanate compound (B) and the hydroxy(meth)acrylate compound (C) to produce the thiourethane(meth)acrylate monomer (D); including
In the reaction step, the molar ratio [SH/NCO ] is more than 0.20 and 0.50 or less,
A method for producing a thiourethane (meth)acrylate composition.

According to one aspect of the present disclosure, a thiourethane (meth)acrylate composition, a monomer composition, and a curable composition, which are excellent in bending strength of the cured product and have a reduced polymerization shrinkage rate, and the curable composition Provided are a molded article that is a cured product of a product, and a method for producing a thiourethane (meth)acrylate composition capable of producing the above thiourethane (meth)acrylate composition.

In the present disclosure, a numerical range represented using "to" means a range including the numerical values described before and after "to" as lower and upper limits.
In the present disclosure, the term "step" includes not only independent steps, but also if the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. .
In the present disclosure, when there are multiple substances corresponding to each component in the composition, the amount of each component in the composition is the total amount of the multiple substances present in the composition unless otherwise specified. means.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
In the present disclosure, "light" is a concept that includes active energy rays such as ultraviolet rays and visible light.
In the present disclosure, "(meth)acrylic monomer" means an acrylic monomer or methacrylic monomer, "(meth)acryloyl group" means an acryloyl group or a methacryloyl group, and "(meth)acrylate" means an acrylate or Means methacrylate, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acrylonitrile" means acrylonitrile or methacrylonitrile.
In the present disclosure, "iso(thio)cyanate" means isocyanate or isothiocyanate.
In the present disclosure, -NHC (=O) O- bond and -NHC (=S) O- bond are collectively referred to as "urethane bond", -NHC (= O) O- bond and -NHC (=S) O- A compound containing at least one of the bonds and a (meth)acryloyl group is also called a urethane (meth)acrylate.

[Thiourethane (meth)acrylate composition]
A first embodiment and a second embodiment of the thiourethane (meth)acrylate composition of the present disclosure will be described below.
However, the thiourethane (meth)acrylate composition of one of the first and second embodiments may satisfy the requirements of the thiourethane (meth)acrylate composition of the other embodiment.

<<First embodiment>>
The thiourethane (meth)acrylate composition according to the first embodiment of the present disclosure is
A thiol compound (A) containing two or more mercapto groups, an iso(thio)cyanate compound (B) containing two or more iso(thio)cyanate groups, and a (meth)acrylate compound containing a hydroxy group, hydroxy (meth ) A thiourethane (meth)acrylate composition containing a thiourethane (meth)acrylate monomer (D) which is the reaction product of an acrylate compound (C),
The molar ratio [SH/NCO], which is the ratio of the number of moles of mercapto groups in the thiol compound (A) to the number of moles of iso(thio)cyanate groups in the iso(thio)cyanate compound (B), is greater than 0.20. is 0.50 or less,
A thiourethane (meth)acrylate composition.

The thiourethane (meth)acrylate composition according to the first embodiment is excellent in bending strength of the cured product and has a reduced polymerization shrinkage rate.

As described above, for a composition containing a conventional (meth)acrylate monomer, from the viewpoint of dimensional accuracy of a molded product that is a cured product of the composition, it is necessary to reduce the polymerization shrinkage rate (that is, reduce the volume shrinkage during polymerization). reduction) may be required. On the other hand, when the polymerization shrinkage rate of the composition is reduced, the bending strength of the cured product obtained by curing the composition may be insufficient.
As a result of extensive studies, the present inventors have found that a composition containing the thiourethane (meth)acrylate monomer (D) formed at the above-mentioned molar ratio [SH/NCO] achieves a reduction in the polymerization shrinkage rate. Furthermore, it was found that the bending strength of the cured product was excellent, and as a result, the thiourethane (meth)acrylate composition according to the first embodiment was conceived.

The reason why not only the polymerization shrinkage rate of the thiourethane (meth)acrylate composition according to the first embodiment is reduced but also the bending strength of the cured product is improved is considered as follows.
That is, the fact that the thiourethane (meth)acrylate composition according to the first embodiment has a low polymerization shrinkage rate means that the thiourethane (meth)acrylate monomer (D) itself is difficult to undergo polymerization shrinkage. On the other hand, thiourethane (meth)acrylate monomer (D) has high bending strength. In addition to this high bending strength, the thiourethane (meth)acrylate monomer (D) has the characteristic of having a low polymerization shrinkage rate, so when used in combination with other monomers, the shrinkage stress during curing is generated inside the cured product. It is possible to reduce the amount of residue left behind. This reduction in stress allows the high bending strength of the thiourethane (meth)acrylate monomer (D) to be exhibited at a higher level. As a result, it is presumed that the bending strength as a cured product is improved.

The polymerization shrinkage rate of the thiourethane (meth)acrylate composition according to the first embodiment is, for example, 6.0% or less.
A more preferable range of the polymerization shrinkage rate of the thiourethane (meth)acrylate composition according to the first embodiment can be referred to the second embodiment described later.

In the present disclosure, the polymerization shrinkage rate of the thiourethane (meth)acrylate composition is defined as the polymerization shrinkage rate of the monomer composition containing the thiourethane (meth)acrylate composition and other monomers, and the polymerization shrinkage rate of the other monomer alone. and , respectively, and from these results, the polymerization shrinkage rate of the thiourethane (meth)acrylate composition is calculated (see, for example, Example 101 below).

Specifically, the polymerization shrinkage rate (%) of the thiourethane (meth)acrylate composition in the present disclosure is determined by the following formula (1).

Polymerization shrinkage rate (%) of the thiourethane (meth)acrylate composition={polymerization shrinkage rate C1−polymerization shrinkage rate C2×(1/2)}×2 Formula (1)

In formula (1), the polymerization shrinkage rate C1 is the polymerization shrinkage rate of the curable composition C1, and the polymerization shrinkage rate C2 is the polymerization shrinkage rate of the curable composition C2.
Curable composition C1 contains camphorquinone with respect to the total weight (100 parts by weight) of a monomer composition containing a thiourethane (meth)acrylate composition (50 parts by weight) and triethylene glycol dimethacrylate (50 parts by weight) (0.1 parts by mass) and 2-ethylhexyl 4-(dimethylamino)benzoate (0.4 parts by mass) are added and stirred at 50°C until uniform (for example, at 100 rpm for 10 hours or more). It is a curable composition obtained by
Curable composition C2 is prepared by adding camphorquinone (0.1 parts by mass) and 2-ethylhexyl 4-(dimethylamino)benzoate (0.4 parts by mass) to 100 parts by mass of triethylene glycol dimethacrylate, and uniformly It is a curable composition obtained by stirring at 50° C. until (for example, 100 rpm for 10 hours or more).
The polymerization shrinkage rate C1 and the polymerization shrinkage rate C2 are represented by the following formulas (2) and (3), respectively.

Polymerization shrinkage rate C1=((ρ2 ^C1 −ρ1 ^C1 )/ρ2 ^C1 )×100 Equation (2)
Polymerization shrinkage rate C2=((ρ2 ^C2 −ρ1 ^C2 )/ρ2 ^C2 )×100 Equation (3)

In formula (2), ρ1 ^C1 is the density of the curable composition C1, and ρ2 ^C1 is the density of the cured product of the curable composition C1.
In formula (3), ρ1 ^C2 is the density of curable composition C2, and ρ2 ^C2 is the density of the cured product of curable composition C2.
For the cured product of the curable composition C1, the curable composition C1 is filled into the through holes of a silicon mold having a through hole with a diameter of 15 mm and a through length of 5 mm. Both ends of the through-hole are closed by sandwiching between glass plates, and then the curable composition C1 filled in the mold is irradiated with a visible light irradiation device at an irradiation intensity of 50 mW/cm ² for 3 minutes on each side. It is a cured product with a size of 15 mm in diameter and 5 mm in height obtained by irradiating light through a glass plate (for 6 minutes on both sides together).
The cured product of the curable composition C2 is obtained by filling the through holes of a silicon mold having a through hole with a diameter of 15 mm and a through length of 5 mm. Both ends of the through-hole are closed by sandwiching between glass plates, and then the curable composition C1 filled in the mold is irradiated with a visible light irradiation device at an irradiation intensity of 50 mW/cm ² for 3 minutes on each side. It is a cured product with a size of 15 mm in diameter and 5 mm in height obtained by irradiating light through a glass plate (for 6 minutes on both sides together).

For the thiourethane (meth)acrylate composition according to the first embodiment of the present disclosure, a thiol compound (A) containing two or more mercapto groups and iso(thio)cyanate containing two or more iso(thio)cyanate groups A composition containing a thiourethane (meth)acrylate monomer that is a reaction product of a compound (B) and a hydroxy (meth)acrylate compound (C) that is a (meth)acrylate compound containing a hydroxy group is described above. It is disclosed in Patent Document 1 (International Publication No. 2019/107323).
However, the thiourethane (meth)acrylate composition according to the first embodiment of the present disclosure is a composition produced with a molar ratio [SH/NCO] exceeding 0.20, so the molar ratio [SH/NCO ] is 0.01 to 0.20, which is different from the composition containing the thiourethane (meth)acrylate monomer described in Patent Document 1 (see, for example, paragraph 0021 of the same document).
The thiourethane (meth)acrylate composition according to the first embodiment has the advantage of lower polymerization shrinkage than the composition containing the thiourethane (meth)acrylate monomer described in Patent Document 1, and further has the advantage of being excellent in bending strength when cured (see Tables 2 and 3 in Examples below).

The thiourethane (meth)acrylate composition according to the first embodiment is also advantageous in that it has a high refractive index and is excellent in handleability.
Components in the thiourethane (meth)acrylate composition according to the first embodiment are described below.

<Thiourethane (meth)acrylate monomer (D)>
A thiourethane (meth)acrylate composition according to the first embodiment contains a thiourethane (meth)acrylate monomer (D).
The thiourethane (meth)acrylate monomer (D) contained in the thiourethane (meth)acrylate composition according to the first embodiment may be of only one type, or may be of two or more types.

A thiourethane (meth)acrylate monomer (D) comprises a thiol compound (A) containing two or more mercapto groups, an iso(thio)cyanate compound (B) containing two or more iso(thio)cyanate groups, and a hydroxy group. and a hydroxy (meth)acrylate compound (C), which is a (meth)acrylate compound containing

The thiourethane (meth)acrylate monomer (D) is preferably formed by reacting a mercapto group in the thiol compound (A) with an iso(thio)cyanate group in the iso(thio)cyanate compound (B), containing a thiourethane bond (that is, at least one of -NHC (=O) S- bond and -NHC (=S) S- bond; hereinafter the same) and derived from a hydroxy (meth) acrylate compound (C) Contains (meth)acryloyl groups.
The thiourethane (meth)acrylate monomer (D) is preferably obtained by reacting an iso(thio)cyanate group in the iso(thio)cyanate compound (B) with a hydroxy group in the hydroxy(meth)acrylate compound (C). formed urethane linkages (ie, -NHC(=O)O- linkages and -NHC(=S)O- linkages).

Hereinafter, the thiol compound (A), the iso(thio)cyanate compound (B), and the hydroxy(meth)acrylate compound (C), which are raw materials for forming the thiourethane (meth)acrylate monomer (D), will be described. .

- Thiol compound (A) -
The thiourethane (meth)acrylate monomer (D) is formed using at least one thiol compound (A).

A thiol compound (A) is a compound containing two or more mercapto groups.
The number of mercapto groups in the thiol compound (A) is 2 or more, preferably 3-6, more preferably 3-5, still more preferably 3 or 4.

For the thiol compound (A), for example, the description in paragraphs 0045 to 0087 of WO 2019/107323 can be referred to as appropriate.

As the thiol compound (A);
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "THIOL2"),
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
pentaerythritol tetrakis (2-mercaptoacetate),
Pentaerythritol tetrakis (3-mercaptopropionate) (hereinafter also referred to as "THIOL1"),
2,5-dimercaptomethyl-1,4-dithiane,
Bis(mercaptoethyl) sulfide and diethylene glycol bis(mercaptopropionate)
Preferably at least one selected from the group consisting of;
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
pentaerythritol tetrakis (2-mercaptoacetate) and pentaerythritol tetrakis (3-mercaptopropionate)
At least one selected from the group consisting of is more preferable.

In the following, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane , and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, also referred to as "THIOL3"

- Iso (thio) cyanate compound (B) -
The thiourethane (meth)acrylate monomer (D) is formed using at least one iso(thio)cyanate compound (B).
The iso(thio)cyanate compound (B) is a compound containing two or more iso(thio)cyanate groups.
The number of iso(thio)cyanate groups in the iso(thio)cyanate compound (B) is two or more, preferably two or three, more preferably two.

For the iso(thio)cyanate compound (B), for example, the description in paragraphs 0088 to 0095 of WO 2019/107323 can be appropriately referred to.

As the iso(thio)cyanate compound (B);
hexamethylene diisocyanate,
2,2,4-trimethylhexamethylene diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate,
pentamethylene diisocyanate,
m-xylylene diisocyanate,
1,3-tetramethylxylylene diisocyanate,
isophorone diisocyanate,
bis(isocyanatomethyl)cyclohexane,
bis(isocyanatocyclohexyl)methane,
2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
tolylene diisocyanate,
At least one selected from the group consisting of phenylene diisocyanate and 4,4'-diphenylmethane diisocyanate is preferred.

The iso(thio)cyanate compound (B) has an aromatic It preferably contains a ring.
As the iso(thio)cyanate compound (B) containing an aromatic ring;
m-xylylene diisocyanate,
1,3-tetramethylxylylene diisocyanate,
tolylene diisocyanate,
At least one selected from the group consisting of phenylene diisocyanate and 4,4-diphenylmethane diisocyanate is preferred.

-Hydroxy (meth)acrylate compound (C)-
The thiourethane (meth)acrylate monomer (D) is formed using at least one hydroxy (meth)acrylate compound (C).

A hydroxy (meth)acrylate compound (C) is a (meth)acrylate compound containing a hydroxy group.

For the hydroxy (meth) acrylate compound (C), for example, the description in paragraphs 0096 to 0101 of WO 2019/107323 can be referred to as appropriate.

As the hydroxy (meth)acrylate compound (C);
2-hydroxyethyl (meth)acrylate,
2-hydroxypropyl (meth)acrylate,
2-hydroxybutyl (meth)acrylate,
2-hydroxy-3-phenoxypropyl (meth)acrylate,
At least one selected from the group consisting of 4-hydroxybutyl (meth)acrylate and 1,4-cyclohexanedimethanol mono(meth)acrylate is preferred.

-Mole ratio [SH/NCO]-
In the first embodiment, a thiourethane (meth)acrylate monomer (D) is formed which is a reaction product of a thiol compound (A), an iso(thio)cyanate compound (B), and a hydroxy(meth)acrylate compound (C). When doing, the molar ratio [SH/NCO], which is the ratio of the number of moles of mercapto groups in the thiol compound (A) to the number of moles of iso(thio)cyanate groups in the iso(thio)cyanate compound (B), is It is more than 0.20 and 0.50 or less.
When the molar ratio [SH/NCO] is more than 0.20, effects of reducing the polymerization shrinkage and improving the bending strength of the cured product are exhibited. From the viewpoint of more effectively obtaining the effect of reducing the polymerization shrinkage rate and improving the bending strength of the cured product, the molar ratio [SH/NCO] is preferably 0.21 or more, more preferably 0.23 or more. , and more preferably 0.25 or more.
When the molar ratio [SH/NCO] is 0.50 or less, the viscosity of the formed thiourethane (meth)acrylate monomer (D) and the composition containing the thiourethane (meth)acrylate monomer (D) Since the viscosity is prevented from becoming too high, the operability of the composition is ensured. From the viewpoint of further improving the operability of the composition, the molar ratio [SH/NCO] is preferably 0.45 or less, more preferably 0.40 or less, and still more preferably 0.35 or less.
Here, the molar ratio [SH/NCO] is the charging ratio.

-Mole ratio [(SH + OH) / NCO]-
In the first embodiment, a thiourethane (meth)acrylate monomer (D) is formed which is a reaction product of a thiol compound (A), an iso(thio)cyanate compound (B), and a hydroxy(meth)acrylate compound (C). At the time of The molar ratio [(SH + OH) / NCO], which is the ratio of the total number of moles, is preferably 0.70 to 1.30, more preferably 0.80 to 1.20, and still more preferably 0.90 to 1.10.

There is no particular limitation on the content of the thiourethane (meth)acrylate monomer (D) with respect to the total amount of the thiourethane (meth)acrylate composition according to the first embodiment.
From the viewpoint of more effectively exhibiting the effects of the thiourethane (meth)acrylate composition according to the first embodiment, the content of the thiourethane (meth)acrylate monomer (D) is the thiourethane ( It is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total amount of the meth)acrylate composition.

<Catalyst>
The thiourethane (meth)acrylate composition according to the first embodiment may contain at least one catalyst.
The catalyst used here is the catalyst used to form the thiourethane (meth)acrylate monomer (D) (that is, the thiol compound (A), the iso(thio)cyanate compound (B) and the hydroxy (meth)acrylate compound ( The catalyst used for the reaction with C)) may remain in the composition after formation of the thiourethane (meth)acrylate monomer (D).

Examples of catalysts include:
Organotin compounds such as dibutyltin dilaurate (DBTDL), dibutyltin dioctate, tin octoate;
halogenated tin compounds such as dibutyltin dichloride and dimethyltin dichloride;
Other organometallic compounds other than tin such as copper naphthenate, cobalt naphthenate, zinc naphthenate, zirconium acetylacetonato, iron acetylacetonato and germanium acetylacetonato;
triethylamine, 1,4-diazabicyclo[2.2.2]octane, 2,6,7-trimethyl-1-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undecene, N,N-dimethylcyclohexylamine, pyridine, N-methylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N , N,N',N'-pentamethyldiethylenetriamine, N,N,N',N'-tetra(3-dimethylaminopropyl)-methanediamine, N,N'-dimethylpiperazine, 1,2-dimethylimidazole, etc. Amine compounds and salts thereof;
Trialkylphosphine compounds such as tri-n-butylphosphine, tri-n-hexylphosphine, tricyclohexylphosphine, tri-n-octylphosphine;
etc.
The content of the catalyst is preferably 0.01% by mass to 1% by mass, more preferably 0.03% by mass to 0.7% by mass, relative to the total amount of the thiourethane (meth)acrylate composition, More preferably, it is 0.05% by mass to 0.5% by mass.

<Polymerization inhibitor>
The thiourethane (meth)acrylate composition according to the first embodiment may contain a polymerization inhibitor.
When the thiourethane (meth)acrylate composition according to the first embodiment contains a polymerization inhibitor, the number of polymerization inhibitors contained may be one or two or more.
The polymerization inhibitor is not particularly limited, and examples thereof include dibutylhydroxytoluene (BHT), hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), phenothiazine (PTZ) and the like.

The content of the polymerization inhibitor may be 0.001% by mass to 0.5% by mass, or 0.002% by mass to 0.3% by mass, relative to the total amount of the thiourethane (meth)acrylate composition. , 0.005% by mass to 0.3% by mass, or 0.01% by mass to 0.2% by mass.

The thiourethane (meth)acrylate composition according to the first embodiment may contain components other than the components described above.

There is no particular limitation on the viscosity of the thiourethane (meth)acrylate composition according to the first embodiment.
From the viewpoint of the handling property of the thiourethane (meth)acrylate composition, the viscosity at 65°C of the thiourethane (meth)acrylate composition according to the first embodiment is preferably 100000 mPa s or less. more preferably 60000 mPa·s or less, still more preferably 30000 mPa·s or less, and even more preferably 10000 mPa·s or less.
The lower limit of the viscosity of the thiourethane (meth)acrylate composition according to the first embodiment is not particularly limited, but examples of the lower limit of the viscosity include 1 mPa·s, 10 mPa·s, and 100 mPa·s.

There is no particular limitation on the method for producing the thiourethane (meth)acrylate composition according to the first embodiment.
The thiourethane (meth)acrylate composition according to the first embodiment can be produced, for example, by production method A described below.

<<Second embodiment>>
The thiourethane (meth)acrylate composition according to the second embodiment of the present disclosure is
A thiol compound (A) that is a compound containing two or more mercapto groups, an iso(thio)cyanate compound (B) that is a compound containing two or more iso(thio)cyanate groups, and a (meth)acrylate containing a hydroxy group. containing a hydroxy (meth)acrylate compound (C) as a compound and a thiourethane (meth)acrylate monomer (D) as a reaction product of
The polymerization shrinkage rate is 6.0% or less,
A thiourethane (meth)acrylate composition.

The thiourethane (meth)acrylate composition according to the second embodiment is excellent in bending strength of the cured product and has a reduced polymerization shrinkage rate.
The reason why the thiourethane (meth)acrylate composition according to the second embodiment exhibits the effect of reducing the polymerization shrinkage rate and improving the bending strength of the cured product is that the thiourethane (meth)acrylate composition according to the first embodiment This is the same as the reason why the effect of reducing the polymerization shrinkage and improving the bending strength of the cured product is obtained.

The thiourethane (meth)acrylate composition according to the second embodiment is also advantageous in that it has a high refractive index and excellent handleability.

The thiourethane (meth)acrylate composition according to the second embodiment is
The polymerization shrinkage rate of the thiourethane (meth)acrylate composition is limited to 6.0% or less, and
The same composition as the thiourethane (meth)acrylate composition according to the first embodiment, except that the molar ratio [SH/NCO] is not limited to more than 0.20 and 0.50 or less. The same applies to preferred embodiments.
The thiourethane (meth)acrylate composition according to the second embodiment may satisfy that the molar ratio [SH/NCO] is more than 0.20 and 0.50 or less.

The polymerization shrinkage rate of the thiourethane (meth)acrylate composition according to the second embodiment is preferably 3.0% to 6.0%, more preferably 3.5% to 5.5%, and further It is preferably 4.0% to 5.0%.

There is no particular limitation on the method for producing the thiourethane (meth)acrylate composition according to the second embodiment.
The thiourethane (meth)acrylate composition according to the second embodiment can be produced, for example, by production method A described below.

[Example of method for producing thiourethane (meth)acrylate composition (manufacturing method A)]
An example of a method for producing a thiourethane (meth)acrylate composition (hereinafter referred to as "production method A") is shown below.
Manufacturing method A is
A thiol compound (A) containing two or more mercapto groups, an iso(thio)cyanate compound (B) containing two or more iso(thio)cyanate groups, and a (meth)acrylate compound containing a hydroxy group, hydroxy (meth ) A method for producing a thiourethane (meth)acrylate composition containing a thiourethane (meth)acrylate monomer (D) which is the reaction product of an acrylate compound (C),
a reaction step of reacting a thiol compound (A), an iso(thio)cyanate compound (B) and a hydroxy(meth)acrylate compound (C) to produce a thiourethane (meth)acrylate monomer (D);
In the reaction step, the molar ratio [SH/NCO], which is the ratio of the number of moles of mercapto groups in the thiol compound (A) to the number of moles of iso(thio)cyanate groups in the iso(thio)cyanate compound (B), is more than 0.20 and 0.50 or less,
A method for producing a thiourethane (meth)acrylate composition.

According to production method A, a thiourethane (meth)acrylate composition (for example, the thiourethane (meth)acrylate composition according to the above-described first embodiment and / or second embodiment) that exhibits excellent bending strength of the cured product and has a reduced polymerization shrinkage rate. urethane (meth)acrylate composition) can be produced.

Preferred aspects of each of the thiol compound (A), the iso(thio)cyanate compound (B), the hydroxy(meth)acrylate compound (C), and the thiourethane(meth)acrylate monomer (D) in the production method A are described above. Same as the preferred aspects of each of the thiol compound (A), the iso(thio)cyanate compound (B), the hydroxy(meth)acrylate compound (C), and the thiourethane(meth)acrylate monomer (D) in the first embodiment. is.

<Reaction process>
The reaction step in production method A is to react a thiol compound (A), an iso(thio)cyanate compound (B) and a hydroxy(meth)acrylate compound (C) to produce a thiourethane(meth)acrylate monomer (D). It is a process.
In the reaction step, the above reaction (that is, production of thiourethane (meth)acrylate monomer (D)) is carried out preferably in the presence of a catalyst.

The catalyst is as described above as a component that can be contained in the thiourethane (meth)acrylate composition according to the first embodiment, and preferred aspects are also the same.
The preferred amount of the catalyst to be used (that is, the amount to be charged) is also the same as the preferred content of the catalyst that can be contained in the thiourethane (meth)acrylate composition according to the first embodiment. At this time, the "total amount of the thiourethane (meth)acrylate composition" is defined as the "total amount of the monomers (that is, the thiol compound (A), the iso(thio)cyanate compound (B), and the hydroxy (meth)acrylate compound (C )” (the same applies to the amounts of other components used later).

In the reaction step, the thiol compound (A), iso(thio)cyanate compound (B), and hydroxy(meth)acrylate compound (C) are mixed and reacted.
There is no particular limitation on the manner in which each component is reacted, and all of the components may be mixed at once and reacted, or each component may be divided several times and mixed and reacted.
As a mode of reacting each component, preferably, first, a catalyst, a thiol compound (A), and an iso(thio)cyanate compound (B) are mixed to obtain a thiol compound (A) and an iso(thio)cyanate compound (B). A reaction product (hereinafter referred to as "reaction product AB") is formed, and the hydroxy (meth)acrylate compound (C) is added to the formed reaction product AB, mixed, and reacted. be. At this time, the hydroxy(meth)acrylate compound (C) may be gradually mixed by dropwise addition or the like.

The reaction temperature in the reaction step is preferably 50°C to 120°C, more preferably 60°C to 110°C, still more preferably 70°C to 100°C.

The reaction time in the reaction step is preferably 1 hour or longer, more preferably 5 hours or longer, and still more preferably 10 hours or longer, from the viewpoint of further advancing the reaction.
The reaction time is preferably 30 hours or less from the viewpoint of further suppressing side reactions between the iso(thio)cyanate compounds (B) such as decomposition and polymerization of the thiourethane (meth)acrylate monomer (D). More preferably, it is 25 hours or less.

In the reaction step, the molar ratio [SH/NCO] (details (The same shall apply hereinafter.) is more than 0.20 and not more than 0.50.
A more preferred range of the molar ratio [SH/NCO] is the same as the preferred range of the molar ratio [SH/NCO] in the first embodiment.

In the reaction step, the number of mercapto groups in the thiol compound (A) and the number of hydroxy groups in the hydroxy (meth) acrylate compound (C) with respect to the number of moles of the iso (thio) cyanate groups in the iso (thio) cyanate compound (B) The preferred range of the molar ratio [(SH+OH)/NCO], which is the ratio of the total number of moles, is the same as the preferred range of the molar ratio [(SH+OH)/NCO] in the first embodiment.

In the reaction step, not only the above components but also other components may be added and mixed.
Another component is preferably a polymerization inhibitor. Preferred aspects of the type and usage amount of the polymerization inhibitor are the same as the preferred aspects of the type and usage amount of the polymerization inhibitor in the first embodiment.

Production method A may include other steps than the reaction step.

[Monomer composition]
The monomer compositions of the present disclosure are
the thiourethane (meth)acrylate composition of the present disclosure described above (that is, the thiourethane (meth)acrylate composition according to the first embodiment and/or the second embodiment; the same shall apply hereinafter);
Other monomers (i.e., monomers other than the thiourethane (meth)acrylate monomer (D)),
contains

The monomer composition of the present disclosure contains the thiourethane (meth)acrylate composition of the present disclosure.
Therefore, according to the monomer composition of the present disclosure, the same effect as the aforementioned thiourethane (meth)acrylate composition of the present disclosure can be obtained.

There is no particular limitation on the content of the thiourethane (meth)acrylate monomer (D) relative to the total amount of the monomer composition of the present disclosure.
From the viewpoint of more effectively exhibiting the effects of the monomer composition of the present disclosure, the content of the thiourethane (meth)acrylate monomer (D) is preferably more than 0% by mass and 50% by mass with respect to the total amount of the monomer composition. below, more preferably more than 0% by mass and 30% by mass or less, more preferably more than 0% by mass and 10% by mass or less, still more preferably 1% by mass to 9% by mass, still more preferably 2% by mass % to 8% by mass.

<Other monomers>
Other monomers (that is, monomers other than thiourethane (meth)acrylate monomer (D)) in the monomer composition of the present disclosure include a compound containing an ethylenically unsaturated bond and a thiourethane (meth)acrylate monomer ( Examples include compounds that do not fall under D).
Only one kind of other monomer may be used, or two or more kinds thereof may be used.

For other monomers, for example, the description of the polymerizable compound in paragraphs 0132 to 0183 of WO 2019/107323 can be referred to as appropriate.

The total content of the thiourethane (meth)acrylate monomer (D) and other monomers (that is, the total content of the monomers contained) with respect to the total amount of the monomer composition of the present disclosure is preferably 80% by mass or more, It is more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 97% by mass or more.

- (Meth) acrylate monomer (E) -
As the other monomer, a (meth)acrylate monomer (E) that is a (meth)acrylate monomer other than the thiourethane (meth)acrylate monomer (D) is preferable.

The total content of the thiourethane (meth)acrylate monomer (D) and (meth)acrylate monomer (E) with respect to the total amount of the monomer composition according to the first embodiment is preferably 80% by mass or more, more preferably It is 90% by mass or more, more preferably 95% by mass or more.

(Meth)acrylate monomers (E) include difunctional or higher (meth)acrylate monomers (that is, (meth)acrylate monomers containing two or more (meth)acryloyl groups) and monofunctional (meth)acrylate monomers. and difunctional or higher (meth)acrylate monomers are preferred.
Examples of bifunctional (meth)acrylate monomers include
neopentyl di(meth)acrylate,
1,4-butanediol di(meth)acrylate,
1,6-hexanediol di(meth)acrylate,
1,8-octanediol di(meth)acrylate,
1,9-nonanediol di(meth)acrylate,
1,10-decanediol di(meth)acrylate,
tricyclodecanedimethanol di(meth)acrylate,
ethylene glycol di(meth)acrylate,
diethylene glycol di(meth)acrylate,
triethylene glycol di(meth)acrylate,
tetraethylene glycol di(meth)acrylate,
polyethylene glycol di(meth)acrylate,
tripropylene glycol di(meth)acrylate,
tetrapropylene glycol di(meth)acrylate,
polypropylene glycol di(meth)acrylate,
2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane,
ethylene oxide-modified bisphenol A di(meth)acrylate,
propylene oxide-modified bisphenol A di(meth)acrylate,
2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (UDMA),
etc.

The monomer compositions of the present disclosure are
As the (meth)acrylate monomer (E),
A (meth)acrylate monomer (E1) containing a urethane bond and two or more (preferably two) (meth)acryloyl groups, and
(Meth)acrylate monomer (E2) other than the (meth)acrylate monomer (E1)
It is preferable to contain at least one of
It is more preferred to contain both (meth)acrylate monomer (E1) and (meth)acrylate monomer (E2).
The (meth)acrylate monomer (E2) is preferably a monomer having a lower viscosity than the (meth)acrylate monomer (E1), and contains at least one of an ethyleneoxy group and a propyleneoxy group and two (meth)acryloyl groups ( A meth)acrylate monomer (E2-1) or a (meth)acrylate monomer (E2-2) containing a ring structure and two (meth)acryloyl groups is more preferable.

When the monomer composition of the present disclosure contains both (meth)acrylate monomer (E1) and (meth)acrylate monomer (E2), the monomer composition of the present disclosure contains (meth)acrylate monomer (E1) and (meth) ) Each of the acrylate monomers (E2) may contain only one type, or may contain two or more types.

The (meth)acrylate monomer (E1) includes, for example, an iso(thio)cyanate compound (B) which is a compound containing two or more iso(thio)cyanate groups, and a hydroxy group which is a (meth)acrylate compound containing a hydroxy group. Reaction products with (meth)acrylate compound (C) (eg, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (UDMA)) and the like.

When the monomer composition of the present disclosure contains (meth)acrylate monomer (E1), the content of (meth)acrylate monomer (E1) is the total content of thiourethane (meth)acrylate monomer (D) and other monomers (That is, the total content of the monomers contained) is preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass. .
The upper limit of the content of the (meth)acrylate monomer (E1) depends on the content of the thiourethane (meth)acrylate monomer (D) and the like, but the upper limit is, for example, 95% by mass, 90% by mass, 70% by mass. , 50% by mass, and the like.

Examples of the (meth)acrylate monomer (E2-1) containing at least one of an ethyleneoxy group and a propyleneoxy group and two (meth)acryloyl groups include:
ethylene glycol di(meth)acrylate,
diethylene glycol di(meth)acrylate,
triethylene glycol di(meth)acrylate,
tetraethylene glycol di(meth)acrylate,
polyethylene glycol di(meth)acrylate,
tripropylene glycol di(meth)acrylate,
tetrapropylene glycol di(meth)acrylate,
polypropylene glycol di(meth)acrylate,
etc.

When the monomer composition of the present disclosure contains (meth)acrylate monomer (E2), the content of (meth)acrylate monomer (E2) is the total content of thiourethane (meth)acrylate monomer (D) and other monomers (That is, the total content of the contained monomers), preferably more than 0% by mass and less than 50% by mass, more preferably 1% by mass to 40% by mass, still more preferably 2% by mass to 30% by mass %, more preferably 3% by mass to 20% by mass.

A particularly preferred embodiment of the monomer composition of the present disclosure is
The monomer composition contains a (meth)acrylate monomer (E1) and a (meth)acrylate monomer (E2),
The number of mercapto groups in the thiol compound (A) is 3 or 4,
In this embodiment, the content of the thiourethane (meth)acrylate monomer (D) is more than 0% by mass and 10% by mass or less with respect to the total amount of the monomer composition.

<Other ingredients>
The monomer composition of the present disclosure may contain other components than those mentioned above.
Other components that may be included in the monomer composition of the present disclosure include components in the curable composition described below.

There is no particular limitation on the viscosity of the monomer composition of the present disclosure.
From the viewpoint of the handleability of the monomer composition, the viscosity at 65°C of the monomer composition of the present disclosure is preferably 100000 mPa s or less, more preferably 60000 mPa s or less, and further It is preferably 30000 mPa·s or less, more preferably 10000 mPa·s or less.
The lower limit of the viscosity of the monomer composition of the present disclosure is also not particularly limited, but examples of the lower limit of the viscosity include 1 mPa·s, 10 mPa·s, and 100 mPa·s.

There is no particular limitation on the method of making the monomer composition of the present disclosure.
An example of a method for producing a monomer composition of the present disclosure includes:
providing a thiourethane (meth)acrylate composition of the present disclosure (e.g., producing a thiourethane (meth)acrylate composition by Method A described above);
A step of mixing the prepared thiourethane (meth)acrylate composition with the above-described other monomer (for example, (meth)acrylate monomer (E));
including.

[Curable composition]
The curable composition of the present disclosure contains the thiourethane (meth)acrylate composition of the present disclosure described above or the monomer composition of the present disclosure described above.
That is, the curable composition of the present disclosure contains each component in the thiourethane (meth)acrylate composition of the present disclosure described above or each component in the monomer composition of the present disclosure described above.
The curable composition of the present disclosure consists of the thiourethane (meth)acrylate composition of the present disclosure described above or the monomer composition of the present disclosure described above (that is, the thiourethane (meth)acrylate composition itself of the present disclosure or the monomer composition of the present disclosure itself).

The curable composition of the present disclosure is suitably used for producing cured products (for example, molded articles described below). A cured product as used herein means a product obtained by curing the curable composition of the present disclosure.
Curing of the curable compositions of the present disclosure is accomplished by polymerization of the contained monomers.
Methods for curing the curable composition of the present disclosure include a method of polymerizing the monomers in the curable composition at room temperature, a method of thermally polymerizing the monomers in the curable composition, and a method of photopolymerizing the monomers in the curable composition. and the like.

The curable composition of the present disclosure is excellent in bending strength when cured. Furthermore, since the curable composition of the present disclosure has a low polymerization shrinkage rate when it is formed into a cured product, a cured product with excellent dimensional accuracy can be produced.
It is believed that the thiourethane (meth)acrylate monomer (D) described above contributes to these effects.

The content of the thiourethane (meth)acrylate composition or monomer composition in the curable composition of the present disclosure is preferably 10% by mass or more, more preferably 20% by mass, based on the total amount of the curable composition. That's it.
The content of the thiourethane (meth)acrylate composition or monomer composition in the curable composition of the present disclosure may be 100% by mass, 80% by mass or less, 60% by mass, based on the total amount of the curable composition. % or less, or 50% or less by mass, or the like.

<Polymerization initiator>
The curable composition of the present disclosure preferably contains a polymerization initiator.
When the curable composition of the present disclosure contains a polymerization initiator, the number of polymerization initiators contained may be one, or two or more.
When the curable composition of the present disclosure contains a polymerization initiator, in the process of curing the curable composition, the monomer (i.e., thiourethane (meth) acrylate monomer (D) and optionally contained Other monomers (hereinafter the same) can be further accelerated.

As the polymerization initiator for room-temperature polymerization as polymerization of the monomer, for example, a redox polymerization initiator in which an oxidizing agent and a reducing agent are combined is preferable.
When a redox polymerization initiator is used, for example, separately packaged oxidizing agent and reducing agent may be prepared and mixed immediately before use.

The oxidizing agent is not particularly limited. Oxyketals (1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, etc.), ketone peroxides (methyl ethyl ketone peroxide, etc.), organic peroxides such as hydroperoxides ( t-butyl hydroperoxide, etc.).

The reducing agent is not particularly limited, and tertiary amines (N,N-dimethylaniline, etc.) are usually used.

In addition to these organic peroxide/amine systems, redox polymerization such as cumene hydroperoxide/thiourea system, ascorbic acid/Cu ²⁺ salt system, organic peroxide/amine/sulfinic acid (or its salt) system, etc. An initiator can be used.
Moreover, as a polymerization initiator, tributyl borane, organic sulfinic acid and the like are preferably used.

When thermal polymerization is performed by heating as the polymerization of the monomer, the polymerization initiator is preferably a peroxide, an azo compound, or the like.
The peroxide is not particularly limited, and examples thereof include benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide and the like.
The azo compound is not particularly limited, and examples thereof include azobisisobutyronitrile.

Polymerization initiators (hereinafter also referred to as "photopolymerization initiators") when performing photopolymerization by visible light irradiation as polymerization of monomers include α-diketones/tertiary amines, α-diketones/aldehydes, and α-diketones. A redox initiator such as /mercaptan is preferred.
The photopolymerization initiator is not particularly limited, and examples thereof include α-diketone/reducing agent, ketal/reducing agent, thioxanthone/reducing agent and the like.
Examples of α-diketones include camphorquinone and the like.
Ketals include, for example, benzyl dimethyl ketal and the like.
Thioxanthone includes, for example, 2-chlorothioxanthone.
Examples of reducing agents include tertiary amines (Michler-ketone, etc.), aldehydes (citronellal, etc.), compounds having a thiol group (2-mercaptobenzoxazole, etc.);
etc. can be mentioned.
Furthermore, an initiator of α-diketone/organic peroxide/reducing agent system, which is obtained by adding an organic peroxide to these redox initiators, is also preferably used.

When photopolymerization is performed by ultraviolet irradiation, photopolymerization initiators such as benzoin alkyl ether and benzyl dimethyl ketal are preferred. Photopolymerization initiators of (bis)acylphosphine oxides are also preferably used.

(Bis)acylphosphine oxides include acylphosphine oxides (2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.), bisacylphosphine oxides (bis-(2,6-dichlorobenzoyl)phenylphosphine fin oxide, etc.).
These (bis)acylphosphine oxide photopolymerization initiators may be used alone or in combination with reducing agents such as various amines, aldehydes, mercaptans and sulfinates.
These (bis)acylphosphine oxide photopolymerization initiators may be used in combination with the above visible light photopolymerization initiators.

For example, a polymerization initiator may be used with reference to International Publication No. 2019/107323, International Publication No. 2020/040141, and the like.

The content of the polymerization initiator is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 5% by mass, based on the total amount of monomers contained in the curable composition.

<Filler>
The curable compositions of the present disclosure may contain fillers.
When the curable composition of the present disclosure contains fillers, the number of fillers contained may be one, or two or more.
When the curable composition of the present disclosure contains a filler, the bending strength of the cured product is further improved.

Fillers are roughly classified into organic fillers and inorganic fillers.
Examples of organic fillers include fine powders such as polymethyl methacrylate.

Examples of inorganic fillers include various glasses (mainly composed of silicon dioxide and optionally containing oxides of heavy metals, boron, aluminum, etc.), various ceramics, diatomaceous earth, kaolin, and clay minerals (montmorillonite, etc.). , activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide and hydroxyapatite.
Specific examples of inorganic fillers include barium borosilicate glass, strontium boroaluminosilicate glass, lanthanum glass, fluoroaluminosilicate glass, and boroaluminosilicate glass.

For example, fillers may be used with reference to WO2019/107323, WO2020/040141, and the like.

The content of the filler is preferably 10 parts by mass to 2000 parts by mass, more preferably 50 parts by mass to 1000 parts by mass, more preferably when the total amount of the monomers contained in the curable composition is 100 parts by mass. is 100 parts by mass to 600 parts by mass.

<Other ingredients>
The curable compositions of the present disclosure may contain other ingredients than those mentioned above.
Other ingredients include pigments, dyes, bactericides, disinfectants, stabilizers, preservatives, and the like.

<Preferred uses>
There are no particular restrictions on the uses of the curable compositions of the present disclosure.
The curable composition of the present disclosure can be used, for example, as a paint, coating film-forming composition, dental material composition, and the like.

The curable composition of the present disclosure is excellent in bending strength when cured. Furthermore, since the curable composition of the present disclosure has a low polymerization shrinkage rate when it is formed into a cured product, a cured product with excellent dimensional accuracy can be produced.
Therefore, the curable composition of the present disclosure is particularly suitable as a composition for dental materials.
Here, the dental material composition refers to the dental material composition itself, a cured product of the dental material composition (for example, a molded product described later), or a product obtained by further processing the above cured product, which is used as a dental material. means a composition capable of
Dental materials include dental restorative materials, denture base resins, denture base lining materials, impression materials, luting materials (resin cement, resin-added glass ionomer cement, etc.), dental adhesives (orthodontic adhesives, materials, adhesives for coating cavities, etc.), tooth fissure sealing materials, resin blocks for CAD/CAM, temporary crowns, artificial tooth materials, and the like.
Examples of dental restorative materials include composite resins for dental crowns, composite resins for filling carious cavities, composite resins for building abutments, composite resins for filling restorations, and the like.

<Example of manufacturing method>
There is no particular limitation on the manufacturing method for manufacturing the curable compositions of the present disclosure.
An example of a method for producing the curable composition of the present disclosure is described below.
A method for producing a curable composition of the present disclosure includes, for example, the steps of providing a thiourethane (meth)acrylate composition of the present disclosure or a monomer composition of the present disclosure; and mixing the product with other ingredients (eg, polymerization initiators, fillers, etc.).
The method of making the curable composition of the present disclosure may optionally include other steps.

The step of providing a thiourethane (meth)acrylate composition of the disclosure or a monomer composition of the disclosure simply provides a pre-made thiourethane (meth)acrylate composition of the disclosure or a monomer composition of the disclosure. It may be a process of producing the thiourethane (meth)acrylate composition of the present disclosure or the monomer composition of the present disclosure.
The thiourethane (meth)acrylate composition of the present disclosure can be produced, for example, according to the above-described production method A (that is, an example of the method for producing a thiourethane (meth)acrylate composition), and the monomer composition of the present disclosure is, for example, It can be produced according to one example of the production method of the monomer composition of the present disclosure described above.

[Molded body]
The molded article of the present disclosure is a cured product of the curable composition of the present disclosure described above.
Therefore, the molded article of the present disclosure has excellent bending strength. Furthermore, since the molded article of the present disclosure is a cured product of the curable composition of the present disclosure with reduced polymerization shrinkage, it also has excellent dimensional accuracy.
A molded article is produced, for example, by molding the curable composition of the present disclosure into a desired shape and then curing the molded article.
Examples of methods for curing the curable compositions of the present disclosure have been described above.

Examples (including production examples) of the present disclosure are shown below, but the present disclosure is not limited to the following examples.

[Abbreviation of compounds in Production Examples]
Abbreviations of compounds in Production Examples are shown below.
HPA: 2-hydroxypropyl acrylate XDI: m-xylylene diisocyanate THIOL1: pentaerythritol tetrakis (3-mercaptopropionate)
THIOL2: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane THIOL3: 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercapto Mixture of methyl-1,11-dimercapto-3,6,9-trithiundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane DBTDL: dibutyltin dilaurate BHT: dibutyl hydroxy toluene

[Method for measuring refractive index of thiourethane (meth)acrylate composition in Production Example]
The refractive index of the thiourethane (meth)acrylate composition in each production example was measured at a wavelength of 589.3 nm using an Abbe full digital refractive index system (Abbemat 550 manufactured by Anton Paar). The temperature was controlled at 25°C.

[Production Example 1]
<Production of thiourethane (meth)acrylate composition containing thiourethane acrylate (TUA-1)>
DBTDL (0.1 parts by mass) as a polymerization catalyst and BHT as a polymerization inhibitor are placed in a 100 mL four-necked flask (hereinafter also referred to as a “reactor”) equipped with sufficiently dried stirring blades and a thermometer. (0.05 parts by mass), XDI (21.21 parts by mass) as the iso(thio)cyanate compound (B), and THIOL1 (8.25 parts by mass) as the thiol compound (A) were charged and dissolved. to obtain a homogeneous solution, and then reacted at 80° C. for 6 hours to obtain a solution containing reaction product AB (that is, reaction product of iso(thio)cyanate compound (B) and thiol compound (A)). . The resulting solution was heated to 90° C., and HPA (20.54 parts by mass) as the hydroxy(meth)acrylate compound (C) was added dropwise over 1 hour. Since the internal temperature rose due to the heat of reaction during the dropping, the amount of dropping was controlled so that the internal temperature was 90° C. or less. After the total amount of HPA was added dropwise, the reaction was carried out for 12 hours while maintaining the reaction temperature at 90°C. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. After completion of the reaction, the product was discharged from the reactor to obtain a thiourethane (meth)acrylate composition (50 g) containing thiourethane acrylate (TUA-1) as the thiourethane (meth)acrylate monomer (D). rice field.

[Production Example 2]
<Production of thiourethane (meth)acrylate composition containing thiourethane acrylate (TUA-2)>
A thiourethane (meth)acrylate composition ( 50 g).

-Changes from Production Example 1-
- The type of thiol compound (A) was changed as shown in Table 1.
- The charged amounts of the iso(thio)cyanate compound (B), the thiol compound (A), and the hydroxy(meth)acrylate compound (C) are 22.27 parts by mass, 6.17 parts by mass, and 21.56 parts, respectively. Changed to parts by weight.
- The reaction time until obtaining a solution containing the reaction product AB (that is, the reaction product of the iso(thio)cyanate compound (B) and the thiol compound (A)) was changed from 6 hours to 4 hours.
- The reaction time after dropping the entire amount of the hydroxy (meth) acrylate compound (C) was changed from 12 hours to 10 hours.

[Production Example 3]
<Production of thiourethane (meth)acrylate composition containing thiourethane acrylate (TUA-3)>
A thiourethane (meth)acrylate composition ( 50 g).

-Changes from Production Example 1-
- The type of thiol compound (A) was changed as shown in Table 1.
- The charged amounts of the iso(thio)cyanate compound (B), the thiol compound (A), and the hydroxy(meth)acrylate compound (C) are 22.12 parts by mass, 6.46 parts by mass, and 21.42 parts, respectively. Changed to parts by weight.
- The reaction time until obtaining a solution containing the reaction product AB (that is, the reaction product of the iso(thio)cyanate compound (B) and the thiol compound (A)) was changed from 6 hours to 4 hours.
- The reaction time after dropping the entire amount of the hydroxy (meth) acrylate compound (C) was changed from 12 hours to 10 hours.

[Production Example 4 (Comparative Example)]
<Production of thiourethane (meth)acrylate composition containing thiourethane acrylate (TUA-4)>
A thiourethane (meth)acrylate composition (50 g) containing the comparative monomer thiourethane acrylate (TUA-4) was obtained in the same manner as in Production Example 3 except for the following changes.

-Changes from Production Example 3-
- The charged amounts of the iso(thio)cyanate compound (B), the thiol compound (A), and the hydroxy(meth)acrylate compound (C) are 21.35 parts by mass, 2.09 parts by mass, and 26.56 parts, respectively. Changed to parts by weight.

In Table 1 below, in Production Examples 1 to 4,
type of thiourethane (meth)acrylate monomer (D) or a comparative monomer;
type of thiol compound (A),
type of iso(thio)cyanate compound (B),
type of hydroxy (meth)acrylate compound (C),
molar ratio [SH/NCO] (that is, the ratio of the number of moles of mercapto groups in thiol compound (A) to the number of moles of iso(thio)cyanate groups in iso(thio)cyanate compound (B)), and thiourethane The refractive index at 25 degreeC of a (meth)acrylate composition is shown.

In Table 1, in particular, by comparing Production Example 3 and Production Example 4 (Comparative Example) using the same thiol compound (A) (THIOL3), the molar ratio [SH / NCO] was set to more than 0.20 and 0.50 or less. The thiourethane (meth)acrylate composition of Production Example 3 produced was the thiourethane (meth)acrylate composition of Production Example 4 (comparative example) produced with a molar ratio [SH/NCO] of 0.20 or less. Comparatively, the refractive index was high.
As a result, a thiourethane (meth)acrylate composition containing the thiourethane acrylate (TUA-3) of Production Example 3 and a thiourethane (meth)acrylate composition containing the thiourethane acrylate (TUA-4 (comparative)) of Production Example 4 (comparative example) It was confirmed that the composition was different from the urethane (meth)acrylate composition.

[Abbreviation of compounds in Examples]
Next, abbreviations of compounds in Examples are shown below.
UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate (manufactured by SARTOMER)
3G: triethylene glycol dimethacrylate CQ: camphorquinone EHA: 2-ethylhexyl 4-(dimethylamino)benzoate γ-MPTS: γ-methacryloxypropyltrimethoxysilane

[Example 1]
<Preparation of monomer composition X>
UDMA (85.5 parts by mass) as a (meth)acrylate monomer (E1) containing a urethane bond and two or more (meth)acryloyl groups;
(Meth)acrylate monomer (E2) other than the (meth)acrylate monomer (E1) [specifically, a (meth)acrylate monomer containing at least one of an ethyleneoxy group and a propyleneoxy group and two (meth)acryloyl groups ( E2-1)] as 3G (9.5 parts by mass),
a thiourethane (meth)acrylate composition (5 parts by mass) containing a thiourethane acrylate (TUA-1) as a thiourethane (meth)acrylate monomer (D);
was placed in a container and stirred at 50°C until uniform to obtain a monomer composition X.

Here, the monomer composition X is
a thiourethane (meth)acrylate monomer (D);
A (meth)acrylate monomer (E) that is a (meth)acrylate monomer other than the thiourethane (meth)acrylate monomer (D) (specifically, (meth)acrylate monomer (E1) and (meth)acrylate monomer (E2)) When,
is a monomer composition comprising

<Preparation of curable composition>
With respect to the total mass (100 parts by mass) of the monomer composition X prepared above, CQ (0.1 parts by mass) as a photopolymerization initiator (α-diketone) and 0 as a photopolymerization initiator (reducing agent) .4 parts by mass of EHA was added and stirred at 50° C. until uniform to obtain a curable composition A.
To the obtained curable composition A (30 parts by mass), γ-MPTS-treated Ferro glass filler 70 parts by mass was blended, stirred, and defoamed to obtain a pasty curable composition B. got

<Measurement and evaluation>
Using the paste-like curable composition B, the following measurements and evaluations were performed.
Table 2 shows the results.

(Bending strength of cured product)
-Preparation of test piece-
Paste-like curable composition B was filled in the through-hole of a stainless steel mold having a through-hole with a size of 25 mm long×2 mm wide×2 mm through length. The paste-like curable composition B filled in the mold was irradiated with a visible light irradiation device (Morita Alpha Light V, irradiation intensity: 50 mW/cm ² ) for 3 minutes on each side (that is, 6 minutes on both sides). By applying light irradiation, a cured product having a size of 25 mm×2 mm×2 mm was obtained. The integrated light amount of this light irradiation is 50×60×6=18000 mJ/cm ² .
The obtained cured product was removed from the mold, and the removed cured product was immersed in distilled water in a sealable sample bottle and held at 37° C. for 24 hours.
A cured product kept for 24 hours was used as a test piece.

-Measurement of bending strength-
Using the above test piece and a universal testing machine (Intesco 210X type testing machine), a three-point bending test was performed under the conditions of a fulcrum distance of 20 mm and a crosshead speed of 1 mm/min, and the bending strength (MPa) of the test piece was measured. .

(Polymerization shrinkage rate of paste-like curable composition B)
The density ρ1 of the paste-like curable composition B was measured using a dry automatic densitometer (AccuPycII 1340 manufactured by Micromeritics).
Next, the paste-like curable composition B is filled into the through-holes of a silicon mold having through-holes with a diameter of 15 mm and a through-length of 5 mm, and in this state, both sides of the mold are sandwiched between glass plates. By doing so, both ends of the through-hole were closed. Next, the paste-like curable composition B filled in the mold was irradiated with a visible light irradiation device (Morita Alpha Light V, irradiation intensity 50 mW/cm ² ) for 3 minutes on each side (that is, 6 minutes on both sides in total). minutes) and irradiated with light through a glass plate to obtain a cured product having a size of 15 mm in diameter and 5 mm in height. The integrated light quantity of this light irradiation is also 50×60×6=18000 mJ/cm ² .
The obtained cured product was removed from the mold, and the density ρ2 of the removed cured product was measured using the dry automatic densimeter.
Using ρ1 and ρ2, the polymerization shrinkage rate (%) of the paste-like curable composition B was determined according to the following formula.
The smaller the polymerization shrinkage rate (%), the lower the polymerization shrinkage of the monomer in the composition.

Polymerization shrinkage rate (%) of paste-like curable composition B
= ((ρ2-ρ1)/ρ2)×100

(Polymerization degree (%) of paste-like curable composition B)
FT-IR measurement was performed on the paste-like curable composition B in the state of not being irradiated with light and the state of being irradiated with light for 20 seconds.
FT-IR measurement was performed using an FT-IR Spectrometer (Spectrum two manufactured by PerkinElmer), and light irradiation was performed using Translux (registered trademark) 2Wave (manufactured by Kulzer Japan, irradiation intensity: 1400 mW/cm ² ). rice field. The integrated light amount of this light irradiation is 1400×20=28000 mJ/cm ² .
Based on the results of FT-IR measurement,
The area value of the peak (1660 cm ⁻¹ to 1800 cm ⁻¹ ) derived from the carbon-oxygen double bond (that is, the carbonyl group) in the paste-like curable composition B that is not irradiated with light is determined as AreaCOl,
The area value of the peak (1660 cm ⁻¹ to 1800 cm ⁻¹ ) derived from the carbon-oxygen double bond in the paste-like curable composition B after being irradiated with light for 20 seconds was obtained as AreaCOs,
The area value of the peak (1610 cm ⁻¹ to 1660 cm ⁻¹ ) derived from the carbon-carbon double bond in the paste-like curable composition B that is not irradiated with light is obtained as AreaCCl,
The area value of the peak (1610 cm ⁻¹ to 1660 cm ⁻¹ ) derived from the carbon-carbon double bond in the paste-like curable composition B after being irradiated with light for 20 seconds was determined as AreaCCs.
Based on these results, the degree of polymerization (%) of the curable paste composition B (that is, the conversion rate of carbon-carbon double bonds) was determined by the following formula.

Polymerization degree of paste-like curable composition B (%)
= (1-((AreaCCs/AreaCOs)/(AreaCCl/AreaCOl))) x 100

(Operability of paste-like curable composition B)
A sample bottle with a capacity of 20 mL was filled with the curable paste composition B, and using a ceramic spatula, the operability of the curable paste composition B was evaluated according to the following evaluation criteria.

-Operability of paste-like curable composition B-
A: The viscosity of the paste-like curable composition B was very low, and little resistance was felt when stirred with a spatula.
B: Paste-form curable composition B had a low viscosity, and slightly less resistance when stirred with a spatula.
C: The paste-like curable composition B had a high viscosity and gave a strong resistance when stirred with a spatula.

[Examples 2 and 3, and Comparative Examples 1 to 5]
The same operation as in Example 1 was performed except that the types and amounts of the monomers used to prepare the monomer composition were changed as shown in Table 2.
Table 2 shows the results.

As shown in Table 2, the molar ratio [SH/NCO ] using a thiourethane (meth)acrylate composition containing a thiourethane (meth)acrylate monomer (D) (specifically, TUA-1 to TUA-3) obtained by reacting in Example 1 to In No. 3, the bending strength of the cured product was excellent, and the polymerization shrinkage rate of the paste-like curable composition B was reduced. Moreover, in Examples 1 to 3, the degree of polymerization and operability of the paste-like curable composition B were also excellent.
On the other hand, in place of the thiourethane (meth)acrylate monomer (D), the comparative monomer TUA-4 [specifically, thiol compound (A), iso(thio)cyanate compound (B) and hydroxy (meth) In Comparative Example 2 using a thiourethane (meth)acrylate composition containing a comparative monomer obtained by reacting an acrylate compound (C) at a molar ratio [SH/NCO] of 0.20 or less As compared with Examples 1 to 3, the paste-like curable composition B had a higher polymerization shrinkage rate and a lower bending strength of the cured product.
Further, in Comparative Example 1 using the (meth)acrylate composition containing neither the thiourethane (meth)acrylate monomer (D) nor the above-mentioned comparative monomer, the polymerization shrinkage rate of the paste-like curable composition B was lower than that of Comparative Example 2. was even higher.

[Example 101]
<Preparation of monomer composition Y>
3G (50 parts by mass) as a (meth)acrylate monomer (E2-1) containing at least one of an ethyleneoxy group and a propyleneoxy group and two (meth)acryloyl groups;
A thiourethane (meth)acrylate composition (50 parts by mass) containing a thiourethane acrylate (TUA-1) as a thiourethane (meth)acrylate monomer (D);
was placed in a container and stirred at 50°C until uniform to obtain a monomer composition Y.

Here, the monomer composition Y is
a thiourethane (meth)acrylate monomer (D);
a (meth)acrylate monomer (E) (specifically, a (meth)acrylate monomer (E2-1)) that is a (meth)acrylate monomer other than the thiourethane (meth)acrylate monomer (D);
is a monomer composition comprising

<Preparation of curable composition C1>
With respect to the total mass (100 parts by mass) of the monomer composition Y prepared above, CQ (0.1 parts by mass) as a photopolymerization initiator (α-diketone) and 0 as a photopolymerization initiator (reducing agent) .4 parts by mass of EHA was added and stirred at 50° C. until uniform to obtain a curable composition C1.

<Polymerization shrinkage rate of thiourethane (meth)acrylate composition containing thiourethane (meth)acrylate monomer (D)>
The polymerization shrinkage rate of the curable composition C1 (hereinafter referred to as polymerization shrinkage rate C1) was obtained by the same method as the evaluation of the polymerization shrinkage rate of the paste-like curable composition B in Example 1 described above.
The polymerization shrinkage rate (hereinafter referred to as polymerization shrinkage rate C2) was similarly determined for the curable composition C2 in Comparative Example 101 described later. Curable composition C2 in Comparative Example 101 is a curable composition containing only 3G as a monomer.
Using the polymerization shrinkage rate C1 and the polymerization shrinkage rate C2, the polymerization shrinkage rate of the thiourethane (meth)acrylate composition containing the thiourethane (meth)acrylate monomer (D) was determined according to the following formula.
Table 3 shows the results.

Polymerization shrinkage rate of thiourethane (meth)acrylate composition containing thiourethane (meth)acrylate monomer (D) = {polymerization shrinkage rate C1 - polymerization shrinkage rate C2 x (1/2)} x 2

[Examples 102 and 103]
Except for changing the thiourethane (meth)acrylate composition containing TUA-1 as the thiourethane (meth)acrylate monomer (D) to a thiourethane (meth)acrylate composition containing the monomers shown in Table 3 The same operation as in Example 101 was performed.
Table 3 shows the results.

[Comparative Example 101]
<Preparation of curable composition C2>
(Meth) 3G (100 parts by mass) as the acrylate monomer (E2-1), CQ (0.1 parts by mass) as a photopolymerization initiator (α-diketone) and as a photopolymerization initiator (reducing agent) 0.4 parts by mass of EHA was added and stirred at 50° C. until uniform to obtain a curable composition C2.

<Polymerization shrinkage rate of curable composition C2>
The polymerization shrinkage rate of the curable composition C2 (that is, the polymerization shrinkage rate C2) was obtained by the same method as the evaluation of the polymerization shrinkage rate of the paste-like curable composition B in Example 1 described above.
Table 3 shows the results.

[Comparative Examples 102 and 103]
A thiourethane (meth)acrylate composition containing TUA-1 as the thiourethane (meth)acrylate monomer (D) was treated with other monomers (i.e., UDMA or TUA-4) shown in Table 3 (meth) The same operation as in Example 101 was performed except for changing to an acrylate composition.
Table 3 shows the results.

As shown in Table 3, the molar ratio [SH/NCO ] The thiourethane (meth)acrylate compositions containing the thiourethane (meth)acrylate monomers (D) (that is, TUA-1 to TUA-3) in Examples 101 to 103 obtained by reacting in Comparative Polymerization shrinkage was lower compared to (meth)acrylate compositions containing other monomers (ie, 3G, UDMA, and TUA-4 (comparative)) in Examples 101-103.
From the above results, it can be seen that the monomer composition or curable composition containing the thiourethane (meth)acrylate composition containing the thiourethane (meth)acrylate monomer (D) also has reduced polymerization shrinkage.

Claims (13)

A thiol compound (A) containing two or more mercapto groups, an iso(thio)cyanate compound (B) containing two or more iso(thio)cyanate groups, and a (meth)acrylate compound containing a hydroxy group, hydroxy (meth ) A thiourethane (meth)acrylate composition containing a thiourethane (meth)acrylate monomer (D) which is the reaction product of an acrylate compound (C),
The molar ratio [SH/NCO], which is the ratio of the number of moles of mercapto groups in the thiol compound (A) to the number of moles of the iso(thio)cyanate groups in the iso(thio)cyanate compound (B), is 0. is more than 20 and 0.50 or less,
A thiourethane (meth)acrylate composition. A thiol compound (A) that is a compound containing two or more mercapto groups, an iso(thio)cyanate compound (B) that is a compound containing two or more iso(thio)cyanate groups, and a (meth)acrylate containing a hydroxy group. containing a hydroxy (meth)acrylate compound (C) as a compound and a thiourethane (meth)acrylate monomer (D) as a reaction product of
The polymerization shrinkage rate is 6.0% or less,
A thiourethane (meth)acrylate composition. The thiourethane (meth)acrylate composition according to claim 1 or 2, wherein the thiol compound (A) has three or four mercapto groups. The thiourethane (meth)acrylate composition according to any one of claims 1 to 3, wherein the iso(thio)cyanate compound (B) contains an aromatic ring. The thiourethane (meth) acrylate composition according to any one of claims 1 to 4,
a monomer other than the thiourethane (meth)acrylate monomer (D);
A monomer composition containing A monomer other than the thiourethane (meth)acrylate monomer (D) is a (meth)acrylate monomer (E) that is a (meth)acrylate monomer other than the thiourethane (meth)acrylate monomer (D).
6. A monomer composition according to claim 5. The monomer composition according to claim 5 or 6, wherein the content of the thiourethane (meth)acrylate monomer (D) is more than 0% by mass and 10% by mass or less relative to the total amount of the monomer composition. A monomer other than the thiourethane (meth)acrylate monomer (D) is a (meth)acrylate monomer (E1) containing a urethane bond and two or more (meth)acryloyl groups, and the (meth)acrylate monomer (E1) and a (meth)acrylate monomer (E2) which is a (meth)acrylate monomer of
The number of mercapto groups in the thiol compound (A) is 3 or 4,
The content of the thiourethane (meth)acrylate monomer (D) is more than 0% by mass and 10% by mass or less with respect to the total amount of the monomer composition.
The monomer composition according to any one of claims 5-7. A curable composition containing the thiourethane (meth) acrylate composition according to any one of claims 1 to 4 or the monomer composition according to any one of claims 5 to 8. . Furthermore, the curable composition of Claim 9 containing a polymerization initiator. 11. The curable composition according to claim 9 or 10, which is a dental material composition. A molded article which is a cured product of the curable composition according to any one of claims 9 to 11. A thiol compound (A) containing two or more mercapto groups, an iso(thio)cyanate compound (B) containing two or more iso(thio)cyanate groups, and a (meth)acrylate compound containing a hydroxy group, hydroxy (meth ) A method for producing a thiourethane (meth)acrylate composition containing a thiourethane (meth)acrylate monomer (D) which is the reaction product of an acrylate compound (C),
a reaction step of reacting the thiol compound (A), the iso(thio)cyanate compound (B) and the hydroxy(meth)acrylate compound (C) to produce the thiourethane(meth)acrylate monomer (D); including
In the reaction step, the molar ratio [SH/NCO ] is more than 0.20 and 0.50 or less,
A method for producing a thiourethane (meth)acrylate composition.