JP2019081910A - Polymerizable composition, cured product, and plastic lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable composition capable of producing a plastic lens having a high refractive index and having excellent dispersion stability, a cured product obtained by curing the polymerizable composition, and a plastic lens. A polymerizable composition containing metal oxide particles having a (meth) acryloyl group and a polymerizable compound having an episulfide group. [Selection diagram] None

Description

  The present invention relates to a polymerizable composition, a cured product, and a plastic lens.

Plastic lenses are lighter in weight than glass lenses, excellent in moldability and processability, and high in safety. Therefore, plastic lenses are rapidly spreading in the field of spectacle lenses and occupy most of them.
Such plastic lenses are often obtained by curing a polymerizable composition, and various polymerizable compositions have been proposed. For example, Patent Document 1 discloses a polymerizable composition containing a polymerizable monomer having a functional group and metal oxide particles having a functional group, and examples of the functional group include an isocyanate group and an isothiocyanate. At least one functional group selected from the group consisting of an inert group, a hydroxyl group, an epoxy group, and a thioepoxy group is disclosed.

Patent No. 5350294

On the other hand, in recent years, development of a material having a higher refractive index has been required in order to meet the further demands for thinner and lighter plastic lenses. For example, the cured product obtained from the polymerizable composition described in Patent Document 1 does not satisfy the current higher requirement level, and a further improvement of the refractive index has been necessary.
Further, the polymerizable composition used to form such a plastic lens is also required to have excellent dispersion stability from the viewpoint of industrial productivity.

An object of the present invention is to provide a polymerizable composition capable of manufacturing a plastic lens having a high refractive index and also having excellent dispersion stability in view of the above-mentioned situation.
Moreover, this invention also makes it a subject to provide the hardened | cured material obtained by using the said polymeric composition, and a plastic lens.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved by using a specific functional group as a functional group contained in a metal oxide particle and a polymeric compound, as a result of earnestly examining about the problem of a prior art.
That is, it discovered that the said objective could be achieved by the following structures.

(1) A polymerizable composition comprising a metal oxide particle having a (meth) acryloyl group, and a polymerizable compound having an episulfide group.
(2) The polymerizable composition as described in (1) whose content of a metal oxide particle is 40 mass% or more with respect to solid content total mass.
(3) The polymerizable composition according to (1) or (2), further comprising a solvent.
(4) The polymerizable composition according to (3), wherein the solvent comprises a solvent having an SP value of 15 to 25 (MPa) ^1/2 .
(5) The polymerizable composition according to (3) or (4), wherein the solvent is a ketone solvent.
(6) The polymerizable composition according to any one of (1) to (5), which is used to form a lens.
(7) A cured product formed by using the polymerizable composition according to any one of (1) to (6).
(8) A plastic lens formed of the cured product of (7).

According to the present invention, a plastic lens having a high refractive index can be produced, and a polymerizable composition excellent in dispersion stability can be provided.
Moreover, according to this invention, the hardened | cured material obtained by using the said polymerizable composition, and a plastic lens can be provided.

Below, the polymeric composition of this invention, hardened | cured material, and the suitable aspect of a plastic lens are demonstrated in detail.
In addition, in this specification, the numerical range described by "-" shall contain an upper limit and a lower limit. For example, the numerical range "10 to 20" includes "10" and "20".

The characteristic point of the polymerizable composition of the present invention is that a specific functional group is selected as the functional group contained in the metal oxide particles and the polymerizable compound. More specifically, the metal oxide particles contain (meth) acryloyl groups, and the polymerizable composition contains episulfide groups. Although the details of the reason why the desired effect can be obtained by the polymerizable composition of the present invention are unknown, it is presumed as follows. First, the metal oxide particles function as a catalyst for the ring opening reaction of the episulfide group, a thiol group is generated, and the obtained thiol group and the (meth) acryloyl group react to progress the crosslinking reaction. As a result, a strong covalent bond is formed between the polymerizable compound and the metal oxide particles, the dispersibility of the metal oxide particles is further improved, and as a result, a higher refractive index is obtained.
Further, in the polymerizable composition of the present invention, even when the content of the metal oxide particles is large, precipitation of the metal oxide particles and white turbidity of the polymerizable composition are less likely to occur, and the dispersion stability of the polymerizable composition is stabilized. It is also excellent in
Furthermore, the cured product obtained from the polymerizable composition of the present invention also has a high glass transition temperature.

The polymerizable composition of the present invention at least includes a metal oxide particle having a (meth) acryloyl group and a polymerizable compound having an episulfide group.
Hereinafter, each component contained in the polymerizable composition will be described in detail.

<Metal oxide particles having (meth) acryloyl group>
As a metal oxide particle part used as a base in metal oxide particles which have a (meth) acryloyl group, a metal oxide which has high refractive index can be used conveniently.
Particles of an oxide of at least one metal selected from Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti as metal oxide particles having a high refractive index Preferably it is mentioned. Among them, particles of an oxide containing Ti (titanium oxide particles) are preferable in that the refractive index is high.
The metal oxide particles may contain only one kind of metal (metal atom) exemplified above, or may contain two or more kinds of metal (metal atom).

The average particle size of the metal oxide particles is not particularly limited, but is preferably 1 to 200 nm, and more preferably 5 to 30 nm. If it is in the said range, while being excellent in the dispersion stability of a polymeric composition, the whitening of hardened | cured material can be suppressed more.
In addition, the said average particle diameter measures the diameter of 100 or more metal oxide particle with a transmission type microscope, and calculates | requires them by carrying out the arithmetic mean. When the metal oxide particles are not perfectly circular, the major diameter is taken as the diameter.

The metal oxide particles have a (meth) acryloyl group in order to enhance the dispersion stability in the polymerizable composition and to improve the crosslink density. In addition, a (meth) acryloyl group is the concept containing an acryloyl group and a methacryloyl group.
The method for providing the (meth) acryloyl group to the metal oxide particles is not particularly limited, and known methods can be adopted. For example, when the metal oxide particles are treated with a compound having a (meth) acryloyl group and a functional group (interactive group) capable of interacting with the metal oxide particles, the interactive group in the compound is a metal It can interact with the oxide particle surface to provide a (meth) acryloyl group. In addition, the kind in particular of said interactive group is not restrict | limited, Well-known groups, such as an amino group, a thiol group, a silane group, are mentioned.

<Polymerizable compound having an episulfide group>
The polymerizable compound includes an episulfide group. Only one episulfide group may be contained in the polymerizable compound, or two or more episulfide groups may be contained. It is preferable that 2 or more is contained in the point which the intensity | strength of the hardened | cured material obtained is more excellent.
In addition, an episulfide group represents the functional group by which the oxygen atom in the epoxy group was substituted by the sulfur atom, and may also be called a thio epoxy group and an epithio group.
More specifically, the polymerizable compound has a group represented by the following formula (1).

  As one of the suitable aspects of a polymeric compound, the polymeric compound represented by following (2) Formula is mentioned.

  m is an integer of 0 to 4; n is an integer of 0 to 1;

In addition, as a polymerizable monomer which has such an episulfide group, the thing described in stage-of Unexamined-Japanese-Patent No. 2004-345123 can be used conveniently.
Among them, bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1 , 3-bis (β-epithiopropylthio) propane, 1,4-bis (β-epithiopropylthio) butane, 1,4-bis (β-epithiopropylthiomethyl) benzene, 2,5-bis An episulfide compound having two episulfide groups such as (.beta.-epithiopropylthiomethyl) -1,4-dithiane in a molecule is preferably mentioned.
In addition, only 1 type of polymerizable compounds may be contained in a polymerizable composition, and 2 or more types of polymerizable compounds may be contained.

<Any ingredient>
The polymerizable composition may contain other components other than the metal oxide particles and the polymerizable compound described above. Hereinafter, optional components that may be contained in the polymerizable composition will be described in detail.

  The polymerizable composition may contain a thiol compound. As a thiol compound, SH having at least one SH group in one molecule described in JP-A-2004-315556, such as aliphatic polythiol compounds, aromatic polythiol compounds, mercapto group-containing cyclic compounds, mercapto group-containing sulfide compounds, etc. Group-containing organic compounds can be mentioned.

The polymerizable composition may contain a solvent. The solvent may be water or an organic solvent.
The type of the organic solvent is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, ether solvents such as diethyl ether, tetrahydrofuran and ethylene glycol dimethyl ether, methyl acetate, butyl acetate Ester solvents such as benzyl benzoate, dimethyl carbonate, ethylene carbonate, γ-butyrolactone and caprolactone, hydrocarbon solvents such as benzene, toluene, ethylbenzene and tetralin, halogenated hydrocarbon solvents such as dichloromethane, trichloroethane and chlorobenzene, Amide or cyclic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone (N-methyl-2-pyrrolidone), dimethyl Sulfone solvents such as sulfonic, sulfoxide solvents such as dimethyl sulfoxide can be exemplified.
Among them, ketone solvents are preferable and methyl ethyl ketone is more preferable in that the dispersion stability of the polymerizable composition is more excellent.

In addition, a solvent having an SP value of 15 to 25 (MPa) ^1/2 is preferable, and a solvent having an SP value of 17 to 23 (MPa) ^1/2 is more preferable, in that the dispersion stability of the polymerizable composition is more excellent. And solvents of 18 to 21 (MPa) ^1/2 are more preferred.
The SP value in the present invention is a solubility parameter of 25 ° C. In the present specification, the solubility parameter is the Hansen SP value and is calculated by Hansen, Charles (2007). Hansen Solubility Parameters: A user's handbook, second edition. Boca Raton, Fla: CRC Press.

The polymerizable composition may optionally contain a curing agent and a polymerization catalyst.
As described above, in the polymerizable composition, the metal oxide particles are considered to function as a catalyst for the ring opening reaction of the episulfide group, and the curing agent and the polymerization catalyst may not be contained.

  In addition, the polymerizable composition contains, if necessary, various additives such as a light stabilizer, a UV absorber, an antioxidant, a coloring inhibitor, a dye, a filler, and an internal mold release agent. It is also good.

<Polymerizable composition>
The polymerizable composition includes the metal oxide particles having the (meth) acryloyl group described above. The content of the metal oxide particles having a (meth) acryloyl group is not particularly limited, but the refractive index of the cured product is higher and the dispersion stability of the polymerizable composition is more excellent relative to the total mass of the solid content 40 mass% or more is preferable, 40-90 mass% is more preferable, 50-80 mass% is more preferable, 50-60 mass% is especially preferable.
In addition, solid content intends the component which can comprise the hardened | cured material mentioned later, for example, the metal oxide particle which has a (meth) acryloyl group, the polymeric compound which has an episulfide group, and a solvent are not contained. .
The content of the metal oxide particles having a (meth) acryloyl group relative to the total mass of the composition is not particularly limited, but the refractive index of the cured product is higher, and the dispersion stability of the polymerizable composition is more excellent. 20 mass% or more is preferable with respect to the thing total mass, 20-40 mass% is more preferable, 20-30 mass% is more preferable, 23-28 mass% is especially preferable.

  The polymerizable composition includes the polymerizable compound having an episulfide group described above. The content of the polymerizable compound having an episulfide group is not particularly limited, but the refractive index of the cured product is higher and the dispersion stability of the polymerizable composition is more excellent. % By mass is preferable, 20 to 50% by mass is more preferable, and 40 to 50% by mass is more preferable.

  In the polymerizable composition, the content of the metal oxide particles having (meth) acryloyl group relative to the total mass of the metal oxide particles having (meth) acryloyl group and the polymerizable compound having episulfide group is not particularly limited. And 40% by mass or more is preferable, 40 to 90% by mass is more preferable, and 50 to 80% by mass is more preferable, in that the refractive index of the cured product is higher and the dispersion stability of the polymerizable composition is more excellent. -60 mass% is especially preferable.

  When the solvent is contained in the polymerizable composition, the content of the solvent is preferably 45 to 70% by mass, based on the total mass of the composition, from the viewpoint that the dispersion stability of the polymerizable composition is more excellent. 65 mass% is more preferable, and 50 to 60 mass% is more preferable.

  The method of preparing the polymerizable composition is not particularly limited, and the polymerizable composition can be prepared by mixing the above-described components according to a known method. Alternatively, a solution containing the above-mentioned metal oxide particles may be prepared first, and then a polymerizable compound may be added thereto.

<Hardened, plastic lens>
In the cured product obtained by polymerizing the above-mentioned polymerizable composition, since the metal oxide particles are uniformly dispersed in the cured product, it is optically transparent and has a desired refractive index. .
The curing method of the polymerizable composition is not particularly limited, and a known curing method is adopted, but a heat curing method of heat treatment is preferable.
The temperature condition in the heat treatment is not particularly limited, and an optimum temperature is selected depending on the material to be used. However, the heating temperature is preferably 80 to 140 ° C., and 100 to 100 from the viewpoint of easy curing. 120 degreeC is more preferable, as heating time, 1 to 50 hours are preferable, and 3 to 45 hours are more preferable.
In addition, the heat treatment may be performed multiple times with different heating conditions.

In addition, since the hardened | cured material obtained by the said hardening process shows a high refractive index, it can apply suitably to a plastic lens. The method for producing the plastic lens is not particularly limited, and a known method is adopted.
In addition, in the plastic lens, both sides of the lens are finished lens which is finished on a predetermined optical surface by transfer from a forming mold, and one side is finished on an optical surface by transferring from a forming mold, and the opposite side is polished Includes a semi-finished lens that is cut to the optical surface by processing.
In addition, a primer layer, a hard coat layer, an antireflective layer and an antifouling layer are formed on the surface of the plastic lens, as necessary.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these.

Example 1
Bis (β-epithiopropyl) disulfide is added to a beaker, and methyl ethyl ketone solution (metal oxide particle concentration) containing metal oxide particles (titanium oxide particles, average particle diameter: 10 nm) having (meth) acryloyl group is further added 30% by mass) and stirring for 30 minutes to obtain a polymerizable composition. In the obtained polymerizable composition, the content relative to the total mass of solid content of metal oxide particles having (meth) acryloyl group is 50% by mass, and the total content of solid content of bis (β-epithiopropyl) disulfide is The content with respect to the mass was 50% by mass, and the content with respect to the total mass of the composition of methyl ethyl ketone (SP value: 19.1 (MPa) ^1/2 ) was 54% by mass.
The resulting polymerizable composition was allowed to stand overnight and left under reduced pressure to evaporate the solvent, and then heat-treated at 100 ° C. for 5 hours to obtain a cured product.

<Various evaluations>
(Dispersion stability)
The polymerizable composition in the beaker after 30 minutes of stirring described above was visually observed from the top of the beaker and evaluated according to the following criteria. Practically, A or B is preferable.
"A": When the bottom of the beaker is visible, there is no aggregate "B": The bottom of the beaker is visible but it is difficult to see, and when the polymerizable composition is slightly cloudy "C": The polymerizable composition is If it is cloudy and you can not see the bottom of the beaker

(Refractive index measurement)
The refractive index of the cured product was measured at 20 ° C. with three light beams (473 nm, 594 nm, 632.8 nm) using Metricon's prism coupler, and the e-line (wavelength 546 nm) was calculated from the result.

(Glass transition temperature measurement)
The glass transition temperature (Tg) of the cured product was measured using a TMA method.

Example 2
The same as Example 1, except that the polymerizable compound to be used was changed from bis (β-epithiopropyl) disulfide to bis (β-epithiopropyl) sulfide, and the amount of each component was changed as shown in Table 1. The cured product was manufactured according to the procedure. The results are summarized in Table 1 below.

In Table 1 below, “disulfide” intends bis (β-epithiopropyl) disulfide, and “sulfide” intends bis (β-epithiopropyl) sulfide.
Also, in Table 1 below, ">150" is intended to be more than 150.

As shown in Table 1, the polymerizable composition of the present invention exhibited excellent dispersion stability, and the obtained cured product exhibited a high refractive index. In addition, the glass transition temperature of the cured product was also high.
In addition, it is confirmed that the refractive index of the hardened | cured material obtained by the Example of patent document 1 is 1.792 at the maximum, and the hardened | cured material obtained from the polymeric composition of this invention shows the outstanding refractive index It was done.

Example 3
Curing according to the same procedure as Example 2, except that the content relative to the total mass of solid content of the metal oxide particles is changed to 60 mass% to 40 mass%, 50 mass%, 70 mass%, and 80 mass%. The object was made.
When the content relative to the total mass of the solid content of the metal oxide particles is 40% by mass, the content relative to the total mass of the solid content of the polymerizable compound is 60 mass%, and the content relative to the total mass of the solvent is 48 It was mass%. In addition, when the content relative to the total mass of the solid content of the metal oxide particles is 50% by mass, the content relative to the total mass of the solid content of the polymerizable compound is 50 mass%, and the content relative to the total mass of the solvent is 54 It was mass%. When the content of the metal oxide particles relative to the total mass of the solid content is 70% by mass, the content of the polymerizable compound relative to the total mass of the solid content is 30% by mass, and the content relative to the total mass of the solvent is 62 It was mass%. When the content relative to the total mass of the solid content of the metal oxide particles is 80 mass%, the content relative to the total mass of the solid content of the polymerizable compound is 20 mass%, and the content relative to the total mass of the solvent is 65 It was mass%.
The polymerizable compositions obtained at contents (50% by mass, 70% by mass, and 80% by mass) show the same dispersion stability "A" as in Example 2, and from the respective polymerizable compositions The cured product exhibited an excellent refractive index.
The polymerizable composition obtained at the content (40% by mass) exhibited the dispersion stability "B", and the cured product formed from each polymerizable composition exhibited an excellent refractive index.
From these results, it was confirmed that the desired effect can be obtained also when the content of the metal oxide particles is changed.

Claims (8)

  The polymeric composition containing the metal oxide particle which has a (meth) acryloyl group, and the polymeric compound which has an episulfide group.   The polymerizable composition according to claim 1, wherein the content of the metal oxide particles is 40% by mass or more based on the total mass of the solid content.   The polymerizable composition according to claim 1, further comprising a solvent. The polymerizable composition according to claim 3, wherein the solvent comprises a solvent having an SP value of 15 to 25 (MPa) ^1/2 .   The polymerizable composition according to claim 3, wherein the solvent is a ketone solvent.   The polymerizable composition according to any one of claims 1 to 5, which is used to form a lens.   A cured product formed using the polymerizable composition according to any one of claims 1 to 6.   A plastic lens formed from the cured product of claim 7.