WO2018168233A1 - Curable composition, cured object, optical member, and lens - Google Patents

Abstract

Provided is a curable composition from which a cured object having a given Abbe number can be molded, the cured object having a partial dispersion ratio (θg, F) higher than a partial dispersion ratio (θg, F) estimated from the Abbe number. The curable composition is excellent in terms of mold transferability. Also provided are the cured object, an optical member, and a lens. The curable composition comprises compound A represented by general formula (A), compound B having at least one fluorine atom and at least one radical-crosslinkable group in the molecule, and at least one initiator selected from among thermo-radical polymerization initiators and photo-radical polymerization initiators.

Description

Curable composition, cured product, optical member and lens

The present invention relates to a curable composition, a cured product, an optical member, and a lens.

Conventionally, glass materials have been used for optical members of imaging modules such as cameras, video cameras, camera-equipped mobile phones, videophones, and camera doorphones. Glass materials have been used preferably because they have various optical properties and are excellent in environmental resistance. However, they have the disadvantages that weight reduction and size reduction are not easy, and workability and productivity are poor. On the other hand, the cured resin can be mass-produced and is excellent in workability, and has recently been used for various optical members.

In recent years, along with the downsizing of imaging modules, there has been a demand for downsizing optical members used in imaging modules. However, as optical members are downsized, problems of chromatic aberration arise. In optical members using a cured resin, it has been studied to correct chromatic aberration by adjusting the Abbe number by adding various additives to the curable composition to change the characteristics after curing.

As a monomer used in a curable composition for producing an optical member, a compound having a fluorene skeleton is used. For example, Patent Document 1 discloses that a curable composition capable of forming a cured product having a low Abbe number can be obtained by using a compound having a fluorene skeleton and a compound having an aromatic ring condensed ring group. It is disclosed. Patent Document 2 discloses an optical material containing a cage-type polysilsesquioxane derivative having a specific structure, a bifunctional (meth) acrylate having a fluorene structure, and a bifunctional fluorine-containing (meth) acrylate. A resin precursor composition is disclosed.

Japanese Patent No. 5940496 JP 2009-161487 A

In a material that can exhibit optical characteristics, the partial dispersion ratio (θg, F) tends to decrease as the Abbe number (νd) of the cured product increases, and the Abbe number (νd) and the partial dispersion ratio (θg, It is known that the value of F) has a negative correlation. However, depending on the use of the cured product, a partial dispersion ratio (θg, F) higher than the predicted partial dispersion ratio (θg, F) in a cured product having a predetermined Abbe number may be required.

However, in Patent Documents 1 and 2, a sufficiently high partial dispersion ratio (θg, F) in a cured product having a predetermined Abbe number has not been obtained. For this reason, development of the curable composition which can shape | mold the hardened | cured material which can exhibit a partial dispersion ratio ((theta) g, F) higher than the estimated partial dispersion ratio ((theta) g, F) is calculated | required.

Also, when molding a cured product, the surface shape of the cured product is required to be highly accurate, and the development of a curable composition excellent in mold transferability is also required.

Therefore, in order to solve such problems of the prior art, the present inventors have a partial dispersion ratio (θg, F) that is higher than the partial dispersion ratio (θg, F) predicted for a cured product having a predetermined Abbe number. The present invention has been studied for the purpose of providing a curable composition capable of forming a cured product having). In addition, the present inventors have also studied for the purpose of providing a curable composition having excellent mold transferability.

The concrete means for solving the above problems are as follows.

[1] Compound A represented by the following general formula (A):
Compound B having at least one fluorine atom and at least one radical crosslinkable group in one molecule;
At least one selected from a thermal radical polymerization initiator and a photo radical polymerization initiator;
A curable composition comprising:

In general formula (A), Ar ¹¹ and Ar ¹² each independently represent an aryl group containing a benzene ring surrounded by a broken line or a heteroaryl group containing a benzene ring surrounded by a broken line as one of condensed rings;
X ¹ , Y ¹ , X ² and Y ² are each independently an oxygen atom, a sulfur atom, a nitrogen atom or a carbon atom, and Z ¹ is a 5- to 7-membered aromatic ring together with X ¹ —C═C—Y ¹ Represents an atomic group that includes at least one selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a carbon atom, and Z ² represents 5 to 7 together with X ² —C═C—Y ² A group of atoms forming a member aromatic ring, the group of atoms including at least one selected from an oxygen atom, a sulfur atom, a nitrogen atom and a carbon atom;
Ar ¹³ and Ar ¹⁴ each independently represent an arylene group containing an aromatic ring surrounded by a broken line or a heteroarylene group containing an aromatic ring surrounded by a broken line, and at least one of Ar ¹³ and Ar ¹⁴ is other than a phenylene group A group of
R ³ to R ⁶ each independently represents a substituent, q and r are each independently an integer of 0 to 4, v is an integer of 0 or more, and the maximum number of v is X ¹ -C = The maximum number of substituents that can be substituted on the ring formed by CY ¹ and Z ¹ , w is an integer of 0 or more, and the maximum number of w is X ² -C = CY ² and Z ² is the maximum number of substituents that can be substituted on the ring formed;
L ¹ and L ² each independently represents a single bond, an oxygen atom or a sulfur atom, and R ¹¹ and R ¹² each independently represent an ether bond, an ester bond, a thioether bond, a thioester bond, an amide bond, a carbonate bond and an alkylene. A linking group containing at least one selected from the group or a single bond, R ²¹ and R ²² each independently represents a hydrogen atom or a methyl group;
When Ar ¹¹ to Ar ¹⁴ are each independently a condensed ring group containing an aromatic ring surrounded by a broken line as one of the condensed rings, a group having L ¹ as a linking group, a group having L ² as a linking group, and R ³ to R ⁶ may be each independently substituted with an aromatic ring surrounded by a broken line, or may be substituted with a condensed ring other than the aromatic ring surrounded by a broken line.
[2] The curable composition according to [1], wherein at least one of Ar ¹³ and Ar ¹⁴ is a condensed ring group including an aromatic ring surrounded by a broken line.
[3] Compound B contains at least one group selected from a fluoroalkyl group, a perfluoroalkyl group, a perfluoroalkylene group and a perfluoroalkyleneoxy group, and at least one radical crosslinkable group in one molecule. The curable composition according to [1] or [2], which is a compound having
[4] The curable composition according to any one of [1] to [3], further containing a non-conjugated vinylidene group-containing compound.
[5] The curable composition according to any one of [1] to [4], comprising a thermal radical polymerization initiator and containing a hydroperoxide compound as the thermal radical polymerization initiator.
[6] A semi-cured product of the curable composition according to any one of [1] to [5], having a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz. .
[7] A cured product of the curable composition according to any one of [1] to [5].
[8] An optical member comprising the cured product according to [7].
[9] A lens comprising the cured product according to [7].

According to the present invention, a curable composition capable of forming a cured product having a partial dispersion ratio (θg, F) higher than an expected partial dispersion ratio (θg, F) in a cured product having a predetermined Abbe number. Can be obtained. Moreover, according to this invention, the curable composition excellent in metal mold | die transferability can be obtained.

Hereinafter, the present invention will be described in detail. The constituent elements described below may be described based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

In the present specification, “(meth) acrylate” represents acrylate and methacrylate, and “(meth) acryloyl” represents acryloyl and methacryloyl. The monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a weight average molecular weight of 1,000 or less.
In addition, in the notation of groups in the present specification, the notation that does not indicate substitution and non-substitution includes those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

(Curable composition)
The curable composition contains a compound A represented by the general formula (A) described later and a compound B having at least one fluorine atom and at least one radical crosslinkable group in one molecule. The curable composition is molded into a cured product having a partial dispersion ratio (θg, F) higher than the predicted partial dispersion ratio (θg, F) in the cured product having a predetermined Abbe number. Can do. Also, it exhibits excellent mold transferability.

The Abbe number (νd) and the partial dispersion ratio (θg, F) of the cured product formed from the curable composition are values measured using an Abbe refractometer (manufactured by Kalnew Optical Industry Co., Ltd.). Specifically, the curable composition is poured into a transparent glass mold having a diameter of 10 mm and a thickness of 1 mm and heated at 200 ° C. in an atmosphere having an oxygen concentration of 1% or less to form a cured product (heating step). The Abbe number (νd) and the partial dispersion ratio (θg, F) are measured for the cured product. The Abbe number (νd) and the partial dispersion ratio (θg, F) of the cured product are calculated by the following equations. In addition, when shape | molding hardened | cured material, it may replace with the said heating process, may employ | adopt an ultraviolet irradiation process, and may employ | adopt both a heating process and an ultraviolet irradiation process.
νd = (nd−1) / (nF−nC)
θg, F = (ng−nF) / (nF−nC)
Here, nd represents a refractive index at a wavelength of 587.56 nm, nF represents a refractive index at a wavelength of 486.13 nm, nC represents a refractive index at a wavelength of 656.27 nm, and ng represents a refractive index at a wavelength of 435.83 nm.

In a cured product having a predetermined Abbe number, the predicted partial dispersion ratio (θg, F) is represented by the Abbe number (νd) based on the d-line as the horizontal axis and the partial dispersion ratio (θg, F) as the vertical axis. In this graph, when the straight line connecting Glass Type A (Ohara Corporation, Glass Type Name NSL7) and Glass Type B (Ohara Corporation, Glass Type PBM2) is the standard line, the partial dispersion ratio (θg, F) on this standard line is there. Glass type A has an Abbe number (νd) of 60.49 and a partial dispersion ratio (θg, F) of 0.5436. Further, the Abbe number (νd) of the glass type B is 36.26, and the partial dispersion ratio (θg, F) is 0.5828. The standard line is a straight line connecting these two points.
Δ (θg, F) is a difference between the partial dispersion ratio (θg, F) of the object and the partial dispersion ratio (θg, F) on the standard line, and is calculated by the following equation.
Δ (θg, F) = Partial dispersion ratio (θg, F) of the object−Partial dispersion ratio (θg, F) on the standard line having the same Abbe number (νd) as the object
It can be said that the higher the value of Δ (θg, F) calculated by the above formula, the higher the partial dispersion ratio (θg, F) than the predicted partial dispersion ratio (θg, F). In the present invention, Δ (θg, F) is preferably 0.040 or more, more preferably 0.046 or more, further preferably 0.060 or more, and 0.080 or more. Is more preferable, and 0.100 or more is particularly preferable. By setting the value of Δ (θg, F) within the above range, it is possible to effectively correct chromatic aberration in a cured product formed from the curable composition of the present invention.

The Abbe number of the cured product formed from the curable composition of the present invention is not particularly limited, but the Abbe number of the cured product is preferably 35 or less, more preferably 30 or less, and 27 More preferably, it is more preferably 25 or less.

The curable composition of the present invention can exhibit excellent mold transferability. Here, the mold transferability can be evaluated based on the yield rate by curing 100 curable compositions and molding 100 cured products. A product with fine irregularities (wrinkles) on the surface of the cured product is evaluated as a defective product, and a product with no unevenness is evaluated as a good product. The non-defective rate is preferably 50% or more, more preferably 70% or more, and further preferably 90% or more. When molding a cured product used for evaluating mold transferability, a composite lens was prepared by the method described in the <Production of composite lens> example, and the appearance of the composite lens was Evaluation is performed using a Keyence digital microscope (trade name: VHX-1000).

The viscosity of the curable composition of the present invention is preferably 20,000 mPa · s or less, more preferably 15,000 mPa · s or less, and further preferably 13,000 mPa · s or less. 000 mPa · s or less is particularly preferable. By setting the viscosity of the curable composition within the above range, it is possible to improve the handling property when molding the cured product and form a high-quality cured product. The viscosity of the curable composition is preferably 2,000 mPa · s or more, more preferably 3,000 mPa · s or more, further preferably 4,000 mPa · s or more, 000 mPa · s or more is particularly preferable.

(Compound A)
A curable composition contains the compound A represented by the following general formula (A).

In general formula (A), Ar ¹¹ and Ar ¹² each independently represent an aryl group containing a benzene ring surrounded by a broken line or a heteroaryl group containing a benzene ring surrounded by a broken line as one of condensed rings.
X ¹ , Y ¹ , X ² and Y ² are each independently an oxygen atom, a sulfur atom, a nitrogen atom or a carbon atom, and Z ¹ is a 5- to 7-membered aromatic ring together with X ¹ —C═C—Y ¹ Represents an atomic group that includes at least one selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a carbon atom, and Z ² represents 5 to 7 together with X ² —C═C—Y ² An atomic group that forms a member aromatic ring, and represents an atomic group that includes at least one selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a carbon atom.
Ar ¹³ and Ar ¹⁴ each independently represent an arylene group containing an aromatic ring surrounded by a broken line or a heteroarylene group containing an aromatic ring surrounded by a broken line, and at least one of Ar ¹³ and Ar ¹⁴ is other than a phenylene group It is the basis of.
R ³ to R ⁶ each independently represents a substituent, q and r are each independently an integer of 0 to 4, v is an integer of 0 or more, and the maximum number of v is X ¹ -C = The maximum number of substituents that can be substituted on the ring formed by CY ¹ and Z ¹ , w is an integer of 0 or more, and the maximum number of w is X ² -C = CY ² and Z ^This is the maximum number of substituents that can be substituted on the ring formed by ² .
L ¹ and L ² each independently represents a single bond, an oxygen atom or a sulfur atom, and R ¹¹ and R ¹² each independently represent an ether bond, an ester bond, a thioether bond, a thioester bond, an amide bond, a carbonate bond and an alkylene. A linking group containing at least one selected from a group or a single bond is represented, and R ²¹ and R ²² each independently represents a hydrogen atom or a methyl group.
When Ar ¹¹ to Ar ¹⁴ are each independently a condensed ring group containing an aromatic ring surrounded by a broken line as one of the condensed rings, a group having L ¹ as a linking group, a group having L ² as a linking group, and R ³ to R ⁶ may be each independently substituted with an aromatic ring surrounded by a broken line, or may be substituted with a condensed ring other than the aromatic ring surrounded by a broken line.

In general formula (A), Ar ¹¹ and Ar ¹² each independently represent an aryl group containing a benzene ring surrounded by a broken line or a heteroaryl group containing a benzene ring surrounded by a broken line as one of condensed rings. Ar ¹¹ and Ar ¹² are preferably each independently an aryl group containing a benzene ring surrounded by a broken line. When Ar ¹¹ and Ar ¹² are aryl groups containing a benzene ring surrounded by a broken line, the aryl group is preferably an aryl group having 6 to 18 carbon atoms, and an aryl group having 6 to 14 carbon atoms More preferably, it is an aryl group having 6 to 10 carbon atoms. Among them, Ar ¹¹ and Ar ¹² are particularly preferably each independently a phenyl group composed of only a benzene ring surrounded by a broken line. When Ar ¹¹ and Ar ¹² are heteroaryl groups containing a benzene ring surrounded by a broken line as one of the condensed rings, the heteroaryl group is preferably a heteroaryl group having 9 to 14 ring members. More preferably, it is a heteroaryl group having 9 to 10 ring members. When Ar ¹¹ and Ar ¹² are heteroaryl groups containing a benzene ring surrounded by a broken line as one of the condensed rings, examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.

In the general formula (A), X ¹ , Y ¹ , X ² and Y ² are each independently an oxygen atom, a sulfur atom, a nitrogen atom or a carbon atom. All of X ¹ , Y ¹ , X ² and Y ² may be carbon atoms, and all of X ¹ , Y ¹ , X ² and Y ² may be atoms other than carbon (from oxygen atoms, sulfur atoms and nitrogen atoms). At least one selected). Further, at least a part of X ¹ , Y ¹ , X ² and Y ² is a carbon atom, and a part of X ¹ , Y ¹ , X ² and Y ² is selected from an oxygen atom, a sulfur atom and a nitrogen atom. One kind may be sufficient.

Z ¹ is an atomic group that forms a 5- to 7-membered aromatic ring with X ¹ —C═C—Y ¹ , and an atom containing at least one selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a carbon atom Z ² represents an atomic group that forms a 5- to 7-membered aromatic ring together with X ² —C═CY ² , and is at least one selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a carbon atom Represents a group of atoms including species. Z ¹ and Z ² are each independently preferably an atomic group containing a carbon atom, and more preferably an atomic group consisting of a carbon atom. Z ¹ is preferably an atomic group that forms a 5- or 6-membered aromatic ring together with X ¹ —C═CY ¹ , and more preferably an atomic group that forms a 6-membered aromatic ring. Z ² is preferably an atomic group that forms a 5- or 6-membered aromatic ring together with X ² —C═C—Y ² , and more preferably an atomic group that forms a 6-membered aromatic ring.

In General Formula (A), Ar ¹³ and Ar ¹⁴ each independently represent an arylene group including an aromatic ring surrounded by a broken line or a heteroarylene group including an aromatic ring surrounded by a broken line. In the case where Ar ¹³ and Ar ¹⁴ are an arylene group containing an aromatic ring surrounded by a broken line, the arylene group is preferably an arylene group having 6 to 18 carbon atoms, and an arylene group having 6 to 14 carbon atoms More preferably, it is an arylene group having 6 to 10 carbon atoms. In addition, when Ar ¹³ and Ar ¹⁴ are heteroarylene groups containing an aromatic ring surrounded by a broken line as one of the condensed rings, the heteroarylene group is preferably a heteroarylene group having 9 to 14 ring members. More preferably, it is a heteroarylene group having 9 to 10 ring members. When Ar ¹³ and Ar ¹⁴ are a heteroarylene group containing an aromatic ring surrounded by a broken line as one of condensed rings, examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.

Here, at least one of Ar ¹³ and Ar ¹⁴ is a group other than a phenylene group. At least one of Ar ¹³ and Ar ¹⁴ is preferably a condensed ring group containing an aromatic ring surrounded by a broken line, or the aromatic ring surrounded by a broken line is a hetero ring. Among them, at least one of Ar ¹³ and Ar ¹⁴ is more preferably a condensed ring group containing an aromatic ring surrounded by a broken line, and examples of the condensed ring group include naphthylene. In particular, Ar ¹⁴ is preferably a condensed ring group containing an aromatic ring surrounded by a broken line. Moreover, it is also preferable that the condensed ring contains a hetero atom, and a nitrogen atom can be illustrated preferably as a hetero atom. Ar ¹³ and Ar ¹⁴ are preferably not the same group. In this case, the other of Ar ¹³ or Ar ¹⁴ is particularly preferably a phenylene group.

In general formula (A), R ³ to R ⁶ each independently represents a substituent. The substituent represented by R ³ to R ⁶ is not particularly limited, and examples thereof include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxyl groups, hydroxyalkyl groups, alkoxy groups, aryl groups, and heteroaryls. A group, an aliphatic ring group, a cyano group, and the like. The substituent represented by R ³ to R ⁶ is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group or a cyano group, and is preferably a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. More preferably a phenyl group or a cyano group, and particularly preferably a halogen atom, a methyl group, a methoxy group, a phenyl group or a cyano group. Among these, R ³ and R ⁴ are preferably each independently a methyl group or a methoxy group, R ⁵ is preferably a halogen atom, a methyl group, or a methoxy group, and R ⁶ is a halogen atom, a methyl group, or a methoxy group. It is preferably a group or a cyano group.

q and r are each independently an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. V is an integer of 0 or more, and the maximum number of v is the maximum number of substituents that can be substituted on the ring formed by X ¹ —C═C—Y ¹ and Z ¹ . v is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. w is an integer of 0 or more, and the maximum number of w is the maximum number of substituents that can be substituted on the ring formed by X ² —C═C—Y ² and Z ² . w is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. In addition, all of q, r, v, and w may be 0. When q is an integer of 2 to 4, the plurality of R ³ may be the same or different, and when r is an integer of 2 to 4, the plurality of R ⁴ may be the same. May be different. When v is an integer of 2 or more, the plurality of R ⁵ may be the same or different, and when w is an integer of 2 or more, the plurality of R ⁶ may be the same or different. Good.

In general formula (A), L ¹ and L ² each independently represents a single bond, an oxygen atom or a sulfur atom. L ¹ and L ² are each independently preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

R ¹¹ and R ¹² each independently represents a linking group containing at least one selected from an ether bond, an ester bond, a thioether bond, a thioester bond, an amide bond, a carbonate bond and an alkylene group, or a single bond. R ¹¹ and R ¹² are each independently a linking group containing at least one selected from an ether bond, an ester bond, a carbonate bond and an alkylene group, or a single bond, preferably a linking group containing an alkylene group. It is more preferable. Among these, it is particularly preferable that R ¹¹ and R ¹² are each independently a linking group composed of an alkylene group. In this case, the alkylene group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.

R ²¹ and R ²² each independently represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

In the case where Ar ¹¹ to Ar ¹⁴ are each independently a condensed ring group containing an aromatic ring surrounded by a broken line as one of the condensed rings, a group having L ¹ as a linking group and a group having L ² as a linking group , And R ³ to R ⁶ may be independently substituted with an aromatic ring surrounded by a broken line or may be substituted with a condensed ring other than the aromatic ring surrounded by a broken line.

Hereinafter, specific examples of the compound A preferably used in the curable composition of the present invention will be listed, but the invention is not limited to the following compounds. In the following structural formulas, MeO represents a methoxy group.

Among them, the compound A is preferably A-1, A-2, A-3, A-4, A-5, A-6, and A-1, A-2, A-3, A-5 A-6 is more preferable, and A-3 and A-6 are particularly preferable.

The content of Compound A in the curable composition is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and more preferably 30 to 60% by mass with respect to the total mass of the curable composition. More preferably, it is mass%. By setting the content of Compound A within the above range, a cured product having a predetermined Abbe number can easily achieve a partial dispersion ratio (θg, F) higher than the predicted partial dispersion ratio (θg, F). Become. Moreover, by setting the content of Compound A within the above range, the curable composition exhibits more excellent mold transferability.

The curable composition may contain two or more compounds A represented by the general formula (A). When 2 or more types of compounds A are contained, the total content is preferably within the above range.

(Compound B)
The curable composition includes Compound B having at least one fluorine atom and at least one radical crosslinkable group in one molecule. By including such a compound, a curable composition excellent in mold transferability can be obtained. Examples of the radical crosslinkable group possessed by Compound B include (meth) acryloyl group, α-fluoroacryloyl group, α-trifluoromethylacryloyl group, allyl group, vinyl group, vinyloxy group and the like. Especially, it is preferable that a radical crosslinkable group is a (meth) acryloyl group or an allyl group.

Compound B may be (1) a monofunctional monomer having at least one fluorine atom and one radical crosslinkable group in one molecule, and (2) at least one fluorine atom and radical crosslinkable in one molecule. It may be a polyfunctional monomer having two or more groups, or (3) a reactive polymer having at least one fluorine atom and a radical crosslinkable group in the side chain. Further, as the compound B, two or more kinds selected from the above (1) monofunctional monomer, (2) polyfunctional monomer, and (3) reactive polymer may be used in combination.

(1) Monofunctional monomers having at least one fluorine atom and one radical crosslinkable group in one molecule include, for example, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) ) Acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, and 2- (perfluorooctyl) ethyl (meth) acrylate.

(2) Examples of the polyfunctional monomer having at least one fluorine atom and two or more radical crosslinkable groups in one molecule include 1,3-bis {(meth) acryloyloxy} -2,2-difluoropropane, 1,4-bis {(meth) acryloyloxy} -2,2,3,3-tetrafluorobutane, 1,5-bis {(meth) acryloyloxy} -2,2,3,3,4,4- Hexafluoropentane, 1,6-bis {(meth) acryloyloxy} -2,2,3,3,4,4,5,5-octafluorohexane, 1,7-bis {(meth) acryloyloxy}- 2,2,3,3,4,4,5,5,6,6-decafluoroheptane, 1,8-bis {(meth) acryloyloxy} -2,2,3,3,4,4,5 , 5,6,6,7,7-dodecaful Looctane, 1,9-bis {(meth) acryloyloxy} -2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorononane, 1, 10-bis {(meth) acryloyloxy} -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane, 1, 11-bis {(meth) acryloyloxy} -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecafluoro Undecane, 1,12-bis {(meth) acryloyloxy} -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10 , 11,11-eicosafluorododecane, 1,8-bis {(meth) acryloyloxy} -2,7-dihydroxy-4,4,5, -Tetrafluorooctane, 1,7-bis {(meth) acryloyloxy} -2,8-dihydroxy-4,4,5,5-tetrafluorooctane, 2,7-bis {(meth) acryloyloxy} -1 , 8-dihydroxy-4,4,5,5-tetrafluorooctane, 1,10-bis {(meth) acryloyloxy} -2,9-dihydroxy-4,4,5,5,6,6,7, 7-octafluorodecane, 1,9-bis {(meth) acryloyloxy} -2,10-dihydroxy-4,4,5,5,6,6,7,7-octafluorodecane, 2,9-bis {(Meth) acryloyloxy} -1,10-dihydroxy-4,4,5,5,6,6,7,7-octafluorodecane, 1,2,7,8-tetrakis {(meth) acryloyloxy} -4 4,5,5-tetrafluorodecane, 1,2,8,9-tetrakis {(meth) acryloyloxy} -4,4,5,5,6,6-hexafluorononane, 1,2,9,10 -Tetrakis {(meth) acryloyloxy} -4,4,5,5,6,6,7,7-octafluorodecane, 1,2,10,11-tetrakis {(meth) acryloyloxy} -4,4 , 5,5,6,6,7,7,8,8-decafluoroundecane, 1,2,11,12-tetrakis {(meth) acryloyloxy} -4,4,5,5,6,6 7,7,8,8,9,9-dodecafluorododecane, 1,10-bis (α-fluoroacryloyloxy) -2,9-dihydroxy-4,4,5,5,6,6,7,7 -Octafluorodecane, 1,9-bis (α-fluoroactene Liloyloxy) -2,10-dihydroxy-4,4,5,5,6,6,7,7-octafluorodecane, 2,9-bis (α-fluoroacryloyloxy) -1,10-dihydroxy-4, 4,5,5,6,6,7,7-octafluorodecane, 1,2,9,10-tetrakis (α-fluoroacryloyloxy) -4,4,5,5,6,6,7,7 -Octafluorodecane, 1,2,11,12-tetrakis (α-fluoroacryloyloxy) -4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorododecane, etc. Can be mentioned. (2) Compounds F-1 to F-30 described in paragraphs 0151 to 0155 and 0160 to 0171 of JP2013-76786A as polyfunctional monomers having two or more radically crosslinkable groups in one molecule F-36 to F-40, F-42 to F-46, F-48 to F-61, F-64 to F-69, F-71 to F-79, F81 to F84, etc. can also be used. .

(3) Examples of the reactive polymer having at least one fluorine atom and radical crosslinkable group in the side chain include the structural unit (a) having a fluorine atom in the side chain and the structural unit having a crosslinkable group in the side chain. Mention may be made of polymers having (b). The molecular weight (weight average molecular weight) of the reactive polymer having a radical crosslinkable group in the side chain is preferably 1,000 to 500,000, more preferably 3,000 to 300,000, More preferably, it is from 000 to 100,000. The weight average molecular weight of the reactive polymer having a radical crosslinkable group in the side chain is a value calculated in terms of standard polystyrene by GPC (Gel Permeation Chromatography) method.

As the structural unit (a) having a fluorine atom in the side chain, a structural unit derived from a monofunctional monomer having one radical crosslinkable group in one molecule of (1) described above can be mentioned. As a structural unit (b) which has a crosslinkable group in a side chain, the structural unit which has the following structures can be mentioned, for example.

In the above structural formulas, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group.

(3) As a structural unit of the reactive polymer having at least one fluorine atom and a radical crosslinkable group in the side chain, a structural unit other than the structural unit (a) and the structural unit (b) may be included. As a structural unit, the structural unit which has an aryl group in a side chain can be mentioned, for example. (3) The compatibility of the compound A and the compound B can be improved because the reactive polymer having a radical crosslinkable group in the side chain further has a structural unit having an aryl group in the side chain. In addition, as a structural unit which has an aryl group in a side chain, the structural unit which has the following structures can be mentioned, for example.

In the above structural formula, Ra represents hydrogen or a methyl group. N represents an integer of 0 to 10, preferably 0 to 2, and more preferably 0 or 1.

Compound B has at least one fluorine atom in one molecule, and has at least one group selected from a fluoroalkyl group, a perfluoroalkyl group, a perfluoroalkylene group, and a perfluoroalkyleneoxy group. Preferably there is. The proportion of fluorine atoms in one molecule of Compound B is preferably 5% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more.

In the following, specific examples of compound B preferably used in the present invention are listed, but are not limited to the following compounds.

The content of Compound B in the curable composition is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and more preferably 20 to 50% with respect to the total mass of the curable composition. More preferably, it is mass%.
The content of fluorine atoms contained in the curable composition is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 7% by mass or more. It is particularly preferable that the content is at least mass%. Moreover, it is preferable that content of the fluorine atom contained in a curable composition is 30 mass% or less. By setting the content of the fluorine atom contained in Compound B and / or the curable composition in the curable composition within the above range, the curable composition can exhibit better mold transferability. it can.

(Other ingredients)
The curable composition may further contain other components in addition to Compound A and Compound B described above. Specific examples of other components include the following. For example, the curable composition further contains a (meth) acrylate monomer described later, a non-conjugated vinylidene group-containing compound, and at least one selected from a photoradical polymerization initiator and a thermal radical polymerization initiator. Also good.

<(Meth) acrylate monomer>
The curable composition may contain a (meth) acrylate monomer. The (meth) acrylate monomer may be a polyfunctional (meth) acrylate monomer having two or more (meth) acryloyl groups in the molecule, and may be a monofunctional (meta) having one (meth) acryloyl group in the molecule. ) May be an acrylate monomer.
Specific examples of the (meth) acrylate monomer include (meth) acrylate monomers described in paragraphs 0037 to 0046 of JP2012-107191A.

Examples of the (meth) acrylate monomer that can be preferably used in the present invention include a monofunctional (meth) acrylate monomer having an aromatic ring represented by monomer 1 (phenoxyethyl acrylate) or monomer 2 (benzyl acrylate), and monomer 3 Examples thereof include a monofunctional (meth) acrylate monomer having an aliphatic ring represented by (tricyclodecane dimethanol diacrylate) or monomer 4 (dicyclopentanyl acrylate). The molecular weight of the (meth) acrylate monomer is preferably 100 to 500.

The method for obtaining the (meth) acrylate monomer is not particularly limited, and may be obtained commercially or may be produced by synthesis. When commercially available, for example, biscoat # 192 PEA (monomer 1) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), biscoat # 160 BZA (monomer 2) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-DCP ( Monomer 3) (manufactured by Shin-Nakamura Chemical Co., Ltd.) and FA-513AS (monomer 4) (manufactured by Hitachi Chemical Co., Ltd.) can be preferably used.

When the curable composition contains a (meth) acrylate monomer, the content of the (meth) acrylate monomer is preferably 1 to 80% by mass with respect to the total mass of the curable composition, and is preferably 2 to 50%. More preferably, it is more preferably 3 to 40% by mass.

<Non-conjugated vinylidene group-containing compound>
The curable composition may include a non-conjugated vinylidene group-containing compound.
As the non-conjugated vinylidene group-containing compound, compounds described in paragraphs 0016 to 0033 of JP2012-107191A can be used. This specification incorporates the contents described in paragraphs 0016 to 0033 of JP2012-107191A.

The molecular weight of the non-conjugated vinylidene group-containing compound is preferably 100 to 400, more preferably 120 to 350, and particularly preferably 130 to 300.

The method for obtaining the non-conjugated vinylidene group-containing compound is not particularly limited, and may be obtained commercially or synthesized. When commercially available, for example, β-caryophyllene (manufactured by Inoue Fragrance Co., Ltd.) and (+)-limonene (manufactured by Tokyo Chemical Industry Co., Ltd.) can be preferably used.

When the curable composition contains a non-conjugated vinylidene group-containing compound, the content of the non-conjugated vinylidene group-containing compound is preferably 0.5 to 30% by mass with respect to the total mass of the curable composition. The content is more preferably 1 to 25% by mass, and further preferably 2 to 20% by mass.

(Polymerization initiator)
The curable composition contains at least one selected from a thermal radical polymerization initiator and a photo radical polymerization initiator.

<Thermal radical polymerization initiator>
The curable composition preferably contains a thermal radical polymerization initiator. Thereby, the hardened | cured material with high heat resistance can be shape | molded by thermally polymerizing a curable composition.

Specifically, the following compounds can be used as the thermal radical polymerization initiator. For example, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, dicumyl peroxide, di-t-butylperoxide, t-butylperoxy-2 -Ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, cumene hydroperoxide, t-butyl hydroperoxide, t-butylperoxy-2-ethylhexyl, 2,3-dimethyl-2,3- And diphenylbutane.

Especially, it is preferable that a curable composition contains a hydroperoxide compound as a thermal radical polymerization initiator. The hydroperoxide compound is a peroxide and a compound having a peroxy group. In the hydroperoxide compound, one oxygen atom of the peroxy group (—O—O—) is substituted with a hydrogen atom, and includes a hydroperoxide group (—O—O—H). A hydroperoxide compound having a hydroperoxide group in the molecule has an effect of promoting chain transfer during the polymerization of the non-conjugated vinylidene group-containing compound, and has more controllability of the three-dimensional structure when the curable composition is cured. It is possible to improve and impart deformability to the semi-cured product.

The method for obtaining the hydroperoxide compound is not particularly limited, and may be obtained commercially or synthesized. When commercially obtained, for example, Park Mill H-80 (cumene hydroperoxide) manufactured by Nippon Oil & Fats Co., Ltd. can be used.

It is preferable that the thermal radical polymerization initiator includes a hydroperoxide compound and another thermal radical polymerization initiator. Examples of other thermal radical polymerization initiators include non-hydroperoxide compounds. Since the hydroperoxide compound generally has a high temperature for initiating thermal radical polymerization, it preferably contains both non-hydroperoxide compounds having a low thermal polymerization initiation temperature. Non-hydroperoxide compounds include t-butyl peroxy-2-ethylhexanoate (Nippon Yushi Co., Ltd., Perbutyl O), t-butyl peroxy-2-ethylhexyl carbonate (Nippon Yushi Co., Ltd., Perbutyl E). It is preferable to use peroxyester compounds such as

The content of the thermal radical polymerization initiator is preferably 0.01 to 10% by mass, more preferably 0.05 to 5.0% by mass, based on the total mass of the curable composition. More preferably, it is 0.05 to 2.0% by mass.

<Radical radical polymerization initiator>
It is preferable that a curable composition contains radical photopolymerization initiator. Specifically, the following compounds can be used as the radical photopolymerization initiator. For example, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,4) 6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,4,4-trimethylpentylphosphine oxide, 1-phenyl-2-hydroxy-2-methyl Propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1,2-diphenylethanedione, methylphenylglyoxylate, 1 -[4- (2-hydroxyethoxy) -phenyl] -2-hydride Xyl-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1 -One, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Examples include amino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. it can.

Among these, as radical photopolymerization initiators, BASF Corporation, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), Irgacure 651 (2,2 -Dimethoxy-1,2-diphenylethane-1-one), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl- 1- (4-methylthiophenyl) -2-morpholinopropan-1-one can be preferably used.

The content of the radical photopolymerization initiator is preferably 0.01 to 5.0% by mass and more preferably 0.05 to 1.0% by mass with respect to the total mass of the curable composition. Preferably, it is 0.05 to 0.5% by mass.
The curable composition preferably contains both a radical photopolymerization initiator and a thermal radical polymerization initiator. In this case, the total content of the radical photopolymerization initiator and the thermal radical polymerization initiator is the curable composition. It is preferably 0.01 to 10% by mass, more preferably 0.05 to 5.0% by mass, and 0.05 to 3.0% by mass with respect to the total mass of the product. Further preferred.

<Polymer having radical polymerizable group in side chain>
The curable composition may further include a polymer having a radical polymerizable group in the side chain, in addition to the above-described compound. However, in this case, the polymer having a radical polymerizable group in the side chain does not contain a fluorine atom. Since the polymer having a radically polymerizable group in the side chain functions to increase the viscosity of the curable composition, it can also be called a thickener or a thickening polymer. In addition, the polymer which has a radically polymerizable group in a side chain can be added when it is necessary to adjust the viscosity of a curable composition in a desired range.

The polymer having a radical polymerizable group in the side chain may be a homopolymer or a copolymer. Especially, it is preferable that the polymer which has a radically polymerizable group in a side chain is a copolymer. When the polymer having a radical polymerizable group in the side chain is a copolymer, it is sufficient that at least one copolymer component has a radical polymerizable group. Further, when the polymer having a radically polymerizable group in the side chain is a copolymer, it includes a monomer unit having a radically polymerizable group in the side chain and a monomer unit having an aryl group in the side chain. More preferably, it is a copolymer.

Examples of the radical polymerizable group include (meth) acrylate group, vinyl group, styryl group, allyl group and the like. The polymer having a radically polymerizable group in the side chain preferably contains 5 to 100% by weight of repeating units having a radically polymerizable group, and more preferably 10 to 90% by weight. 20 to 80% by mass is more preferable.

Specific examples of the polymer having a radically polymerizable group preferably used in the side chain are listed below, but the polymer having a radically polymerizable group in the side chain is not limited to the following structure.
In the following structural formulas, Ra and Rb each independently represent hydrogen or a methyl group. A plurality of Ra in one polymer may be the same or different. N represents an integer of 0 to 10, preferably an integer of 0 to 2, and more preferably 0 or 1.

The molecular weight (weight average molecular weight) of the polymer having a radical polymerizable group in the side chain is preferably 1,000 to 10,000,000, more preferably 5,000 to 300,000. More preferably, it is from 1,000,000 to 200,000. The glass transition temperature of the polymer having a radical polymerizable group in the side chain is preferably 50 to 400 ° C., more preferably 70 to 350 ° C., and further preferably 100 to 300 ° C. .

The content of the polymer having a radical polymerizable group in the side chain is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 25% by mass with respect to the total mass of the curable composition. More preferably, it is% or less. In addition, 0 mass% may be sufficient as content of the polymer which has a radically polymerizable group in a side chain, and the aspect which does not add the polymer which has a radically polymerizable group in a side chain is also preferable.

<Other additives>
Unless it is contrary to the meaning of this invention, the curable composition may contain additives, such as a polymer other than the component mentioned above, a monomer, a dispersing agent, a plasticizer, a heat stabilizer, and a mold release agent.

(Method for producing cured product)
The manufacturing method of hardened | cured material includes the process of photocuring the curable composition mentioned above, and / or the process of thermosetting. Among them, the method for producing a cured product includes a step of forming a semi-cured product by irradiating the curable composition with light or heating the curable composition, and irradiating the obtained semi-cured product with light or semi-cured. A step of forming a cured product by heating the cured product.

<Process for forming semi-cured product>
It is preferable that the step of forming the semi-cured product first includes a transfer step. A transfer process is a process of pressing a metal mold | die against the curable composition mentioned above. In the transfer step, the other mold is pressed against the curable composition injected into one of the pair of molds to spread the curable composition.

It is preferable that the metal mold | die used with the manufacturing method of hardened | cured material is what performed the chromium nitride process. Thereby, a favorable mold releasability can be obtained in a release step performed in a later step, and the manufacturing efficiency of the optical member can be increased.

Examples of the chromium nitride treatment include a method of forming a chromium nitride film on the mold surface. As a method of forming a chromium nitride film on the mold surface, there are, for example, a CVD (Chemical Vapor Deposition) method and a PVD (Physical Vapor Deposition) method. The CVD method is a method of forming a chromium nitride film on a substrate surface by reacting a source gas containing chromium and a source gas containing nitrogen at a high temperature. The PVD method is a method of forming a chromium nitride film on the surface of a substrate using an arc discharge (arc type vacuum deposition method). In this arc type vacuum deposition method, when a cathode (evaporation source) made of, for example, chromium is disposed in a vacuum vessel, an arc discharge is caused between the cathode and the wall of the vacuum vessel via a trigger, and the cathode is evaporated. At the same time, ionization of the metal by arc plasma is performed, a negative voltage is applied to the substrate, and a reaction gas such as nitrogen gas is introduced into the vacuum vessel by about several tens of mTorr (1.33 Pa), thereby bringing the ionized metal and the reaction gas into the substrate It is a method of making a film of a compound by reacting on the surface. The chromium nitride treatment of the mold surface in the present invention is carried out by the above CVD method or PVD method.

Here, in general, the mold can be heated while pressing the contents by combining two molds, and when a low-viscosity composition is injected into the mold, the mold clearance is reached. Cause leakage. For this reason, it is preferable that the curable composition inject | poured into a metal mold | die has a certain viscosity or more. In order to adjust the viscosity of the curable composition, a polymer having the above-described radical polymerizable group in the side chain may be added to the curable composition.

After the step of pressing the mold, a step of forming a semi-cured product is provided. The semi-cured product can be obtained by semi-curing the curable composition injected into the mold. In the step of forming the semi-cured product, light irradiation or heating is performed. In this specification, such a process can also be called a semi-hardening process.

In the step of forming a semi-cured product, at least one of light irradiation and heating is performed on the curable composition to obtain a semi-cured product having a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz. It is preferable to form.

Here, the “semi-cured product” in the present specification is a product obtained by polymerizing a curable composition, which is not completely solid and has a certain degree of fluidity. A product having an upper limit value of complex viscosity of less than 1.0 × 10 ⁹ mPa · s at 25 ° C. and a frequency of 10 Hz can be regarded as a semi-cured product. If the polymer of the curable composition has a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz, the polymer is a semi-cured product. On the other hand, the “cured product” is a product obtained by curing a curable composition by polymerization, and means a product in a completely solid state.

The light used for light irradiation is preferably ultraviolet light or visible light, and more preferably ultraviolet light. For example, a metal halide lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a sterilization lamp, a xenon lamp, an LED (Light Emitting Diode) light source lamp, or the like is preferably used. The atmosphere at the time of light irradiation is preferably air or an inert gas substitution atmosphere, and more preferably an atmosphere substituted with nitrogen until the oxygen concentration becomes 1% or less.

In the semi-curing process, when a heating semi-curing process is provided, the heating semi-curing is performed so that the complex viscosity of the semi-cured product after heating at 25 ° C. and a frequency of 10 Hz is 10 ⁵ to 10 ⁸ mPa · s. preferable.

The present invention also relates to a semi-cured product produced by the method described above. Such a semi-cured product can be preferably used in a method for producing a cured product to be described later. Here, the preferable range of the complex viscosity of the semi-cured product is the same as the preferable range of the complex viscosity of the semi-cured product in the step of forming the semi-cured product.

In the semi-cured product, after the light irradiation step, the radical photopolymerization initiator is completely consumed and may not be contained at all, or the radical photopolymerization initiator may remain.

The glass transition temperature of the semi-cured product is preferably −150 to 0 ° C., more preferably −50 to 0 ° C., and particularly preferably −20 to 0 ° C.

<Step of forming a cured product>
The step of forming a cured product includes a polymerization step in which a semi-cured product is put into a mold and subjected to pressure deformation and heated to thermally polymerize or photopolymerized by light irradiation to obtain a cured product. Is preferred. In this specification, such a process can also be called a hardening process. In addition, the light irradiation conditions and heating conditions in the process of forming the cured product are the same as the conditions in the semi-curing process described above.

When the curing process is a thermal polymerization process, the mold used in the polymerization process is also referred to as a thermoforming mold. In general, it is preferable that the thermoforming mold has a configuration in which two molds can be combined and heated while pressing the contents. Moreover, in the manufacturing method of hardened | cured material, it is more preferable to use a metal mold | die as a shaping | molding die in the thermal polymerization process which obtains hardened | cured material. As such a thermoforming mold, for example, the one described in JP-A-2009-126011 can be used. Moreover, it is preferable that the metal mold has been subjected to a chromium nitride treatment.

In the thermal polymerization step, the semi-cured product placed in the mold is subjected to pressure deformation, heated and thermally polymerized to obtain a cured product. Here, the pressure deformation and the heating may be performed at the same time, the heating may be performed after the pressure deformation, or the pressure deformation may be performed after the heating. It is preferable to carry out simultaneously. Further, it is also preferable that the pressure deformation and the heating are performed at the same time and the heating is further performed at a higher temperature after the pressure is stabilized.

In the thermal polymerization step, the semi-cured product is heated and cured at a temperature of 150 ° C. or higher to obtain a cured product.
The heating temperature is 150 ° C. or higher, preferably 160 to 270 ° C., more preferably 165 to 250 ° C., and still more preferably 170 to 230 ° C.
In this curing step, it is preferable to perform heating and pressure deformation. Thereby, the inverted shape of the inner surface of the mold can be accurately transferred to the cured product.

The pressure in the pressure deformation is preferably 0.098 MPa to 9.8 MPa, more preferably 0.294 MPa to 4.9 MPa, and particularly preferably 0.294 MPa to 2.94 MPa.
The time for the thermal polymerization is preferably 30 to 1000 seconds, more preferably 30 to 500 seconds, and particularly preferably 60 to 300 seconds. The atmosphere at the time of thermal polymerization is preferably air or an inert gas substitution atmosphere, and more preferably an atmosphere substituted with nitrogen until the oxygen concentration becomes 1% or less.

A release step is provided after the curing step. When thermal polymerization is performed in the curing step, it is preferable to pull the mold away from the cured product in the temperature range of 150 to 250 ° C. in the mold release step. By setting the temperature in the mold release step within the above range, the mold can be easily separated from the cured product, and the production efficiency can be increased.

As mentioned above, although an example of the manufacturing method of hardened | cured material was demonstrated, the manufacturing method of hardened | cured material of this invention is not restricted to this, In the range which does not deviate from this invention, it can change suitably. For example, the mold used in the transfer process and the semi-curing process may be used as it is in the curing process. After performing the semi-curing process, the mold is separated from the semi-cured product, and this semi-cured product is separated from another mold. The curing step may be performed by moving to a (thermoforming mold). In this case, it is preferable that the above-described chromium treatment is performed on the mold used in the semi-curing process and the curing process.
In the semi-curing step, the curable composition in the mold may be irradiated with light and heated. Thereby, the semi-hardened material which has a desired degree of hardening can be obtained reliably.

(Semi-cured product)
The present invention also relates to a semi-cured product of the curable composition. The semi-cured product is formed by semi-curing the above-described curable composition. The semi-cured product of the present invention is preferably produced by the above-described method for producing a semi-cured product. The semi-cured product preferably has a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz.

(Cured product)
The present invention also relates to a cured product of the curable composition. The cured product is formed by curing the semi-cured component described above. It is preferable that the hardened | cured material of this invention is manufactured by the manufacturing method of the hardened material mentioned above.

(size)
The cured product of the present invention preferably has a maximum thickness of 0.1 to 10 mm. The maximum thickness is more preferably 0.1 to 5 mm, and particularly preferably 0.15 to 3 mm. The cured product of the present invention preferably has a maximum diameter of 1 to 1000 mm. The maximum diameter is more preferably 2 to 200 mm, and particularly preferably 2.5 to 100 mm.

(Optical member)
The present invention also relates to an optical member including the above-described cured product. Since the hardened | cured material of this invention is a molded object excellent in the optical characteristic, it is preferably used for an optical member. The kind of the optical member of the present invention is not particularly limited. In particular, it can be suitably used as an optical member utilizing the excellent optical characteristics of the curable composition, particularly as an optical member that transmits light (so-called passive optical member). Examples of the optical functional device including such an optical member include various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP (Overhead projector), liquid crystal projector, etc.), optical fiber communication devices (optical waveguide, An optical amplifier etc.), a photographing device such as a camera and a video, etc. are exemplified.

Moreover, as a passive optical member used for an optical functional device, for example, a lens, a prism, a prism sheet, a panel (plate-shaped molded body), a film, an optical waveguide (film-like or fiber-like), an optical disk, and an LED sealing Examples thereof include agents. Such passive optical members include any coating layer, if necessary, such as a protective layer that prevents mechanical damage to the coated surface due to friction and wear, and an undesirable wavelength that causes deterioration of inorganic particles and substrates. Light absorption layer that absorbs light, transmission shielding layer that suppresses or prevents transmission of reactive low molecules such as moisture and oxygen gas, antiglare layer, antireflection layer, low refractive index layer, etc. It may be provided. Specific examples of the optional coating layer include a transparent conductive film and gas barrier film made of an inorganic oxide coating layer, and a gas barrier film and hard coat film made of an organic coating layer. As a coating method for forming the coating layer, a known coating method such as a vacuum deposition method, a CVD method, a sputtering method, a dip coating method, or a spin coating method can be used.

(Application examples)
The optical member using the cured product of the present invention is particularly preferably used for a lens substrate. The lens substrate produced using the curable composition of the present invention has a low Abbe number, and preferably has high refractive properties, light transmittance and light weight, and is excellent in optical properties. In addition, the refractive index of the lens substrate can be arbitrarily adjusted by appropriately adjusting the type of monomer constituting the curable composition.
In the present specification, the “lens substrate” means a single member that can exhibit a lens function. A film or a member can be provided on the surface or the periphery of the lens substrate according to the use environment or application of the lens. For example, a protective film, an antireflection film, a hard coat film, or the like can be formed on the surface of the lens substrate. Moreover, it can be set as the compound lens laminated | stacked on the glass lens base material or the plastic lens base material. Further, the periphery of the lens base material can be fitted and fixed to a base material holding frame or the like. However, these films and frames are members added to the lens base material, and are distinguished from the lens base material itself in this specification.

When the lens substrate is used as a lens, the lens substrate itself may be used alone as a lens, or may be used as a lens by adding the above-described film, frame, or other lens substrate. The type and shape of the lens using the lens substrate are not particularly limited.
The lens base material is preferably used for imaging lenses such as mobile phones and digital cameras, imaging lenses such as televisions and video cameras, vehicle-mounted lenses, and endoscope lenses.

Hereinafter, the features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

(Compound A)
The following compounds were used as Compound A.

<Synthesis of Compound A-1>
Compound A-1 was synthesized according to the method described in Paragraphs 0128 to 0129 of Japanese Patent No. 5940496.

<Synthesis of Compound A-4>
Compound A-4 was synthesized according to the method described in Paragraphs 0132 to 0133 of Japanese Patent No. 5940496.

<Synthesis of Compound A-3>
290 g of 5,6-dimethoxy-1-indanone and 204 g of orthophthalaldehyde were dissolved in 1500 mL of methanol. The reaction solution was heated and maintained at 60 ° C., and 255 g of potassium hydroxide dissolved in 1750 mL of methanol was added dropwise to the reaction solution. After stirring for 5 hours, the reaction solution was returned to room temperature, and the precipitated crystals were collected by filtration to obtain 230 g of Compound 3-1A.

200 g of compound 3-1A and 320 g of phenol were dissolved in 320 mL of methanesulfonic acid. While the reaction solution was heated and maintained at 60 ° C., 3.2 mL of 3-mercaptopropionic acid was added dropwise. After stirring for 5 hours, 720 mL of methanol was added dropwise to the reaction solution. After stirring for 30 minutes, 1400 mL of methanol was further added dropwise. The reaction solution was returned to room temperature, and the precipitated crystals were collected by filtration to obtain 292 g of Compound 3-1B.

To 100 g of 2-hydroxyethyl acrylate, 132 mL of triethylamine and 650 mL of butyl acetate were added and stirred. While maintaining the reaction solution at 5 ° C., 70 mL of methanesulfonic acid chloride was added dropwise over 1 hour. After stirring for 1 hour, 500 mL of water was added to the reaction solution, and after stirring, the operation of removing the aqueous layer was repeated three times. After adding 30 mg of dibutylhydroxytoluene, butyl acetate was distilled off under reduced pressure to obtain 160 g of Compound 3-1C.

To 100 g of compound 3-1B, 500 mL of butyl acetate, 0.5 mL of nitrobenzene, 138 g of potassium carbonate, and 8 g of tetrabutylammonium bromide (TBAB) were added and stirred. To the reaction solution, 150 g of compound 3-1C was added and reacted for 5 hours while maintaining at 80 ° C. Then, 250 mL of toluene was added and stirred. The operation of adding 300 mL of water to the reaction solution and stirring while maintaining the temperature at 60 ° C. was then repeated 3 times. The residue was purified by column chromatography to obtain 120 g of compound A-3.

<Synthesis of Compound A-2>
Compound A-2 was synthesized in the same manner as in the synthesis of Compound A-3 except that 6-methoxy-1-indanone was used instead of 5,6-dimethoxy-1-indanone.

<Synthesis of Compound A-6>
50 mL of ethanol and 10 mL of acetic acid were added to 21.6 g of o-phenylenediamine and 35.6 g of ninhydrin, and reacted at 70 ° C. for 3 hours. After the reaction solution was cooled to room temperature, the precipitated crystals were collected by filtration, washed with ethanol and dried to obtain 40.9 g of Compound 6-1A.

20 g of compound 6-1A and 36 g of 2,6-dimethylphenol were dissolved in 30 mL of methanesulfonic acid. While the reaction solution was heated and maintained at 100 ° C., 0.3 mL of 3-mercaptopropionic acid was added dropwise. After stirring for 3 hours, 70 mL of toluene was added dropwise to the reaction solution. After stirring for 30 minutes, 140 mL of toluene was further added dropwise. The reaction solution was returned to room temperature, and the precipitated crystals were collected by filtration to obtain 29 g of compound 6-1B.

Compound A-6 was synthesized in the same manner as in the synthesis of Compound A-3 except that Compound 6-1B was used instead of Compound 3-1B.

<Synthesis of Compound A-8>
Compound A-8 was synthesized in the same manner as in the synthesis of Compound A-6 except that 4,5-diazafluoren-9-one (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of Compound 6-1A.

(Comparative Compound A)
The following compound RA-1 was used as comparative compound A.

<Synthesis of Compound RA-1>
Compound RA-1 was synthesized according to the method described in paragraph 0097 of Japanese Patent No. 5898551.

(Compound B)
The following compounds were used as Compound B.

Compound B-1: 2,2,2-trifluoroethyl acrylate (manufactured by Tokyo Chemical Industry)
Compound B-2: 2,2,3,3,3-pentafluoropropyl acrylate (manufactured by Tokyo Chemical Industry)
Compound B-3: 1H, 1H, 5H-octafluoropentyl acrylate (Osaka Organic Chemical Co., Ltd., Biscoat 8F)
Compound B-4: Diacrylic acid 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (manufactured by Tokyo Chemical Industry)

<Synthesis of Compound B-5>
Compound B-5 was synthesized according to the method described in paragraphs 0177 to 0180 of JP2013-181140A.

<Synthesis of Compound B-6>
1H, 1H, 5H-octafluoropentyl methacrylate (Osaka Organic Chemical Co., Ltd., Viscoat 8FM) 25.0 g, benzyl methacrylate (Osaka Organic Industry Co., Ltd.) 5.0 g, allyl methacrylate (Wako Pure Chemical Industries, Ltd.) 20.0 g (made by company) was dissolved in 150.0 g of methyl ethyl ketone and heated to 70 ° C. To this solution, a solution prepared by dissolving 0.96 g of a polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 12.0 g of methyl ethyl ketone was dropped over 30 minutes. After completion of dropping, the reaction was further carried out at 70 ° C. for 4.5 hours. The reaction solution was allowed to cool and then added dropwise to 900.0 g of hexane, and the precipitated powder was collected by filtration and dried. In this way, 41.0 g of polymer B-6 was obtained. The weight average molecular weight of the obtained polymer was 33,900 in terms of standard polystyrene by GPC (Gel Permeation Chromatography) method, and the dispersity (Mw / Mn) was 3.2.

<Synthesis of Compound B-7>
1H, 1H, 5H-Octafluoropentyl methacrylate (Osaka Organic Chemical Co., Ltd., Viscoat 8FM) 5.0 g, benzyl methacrylate (Osaka Organic Industry Co., Ltd.) 25.0 g, and allyl methacrylate (Wako Pure Chemical Industries, Ltd.) 20.0 g (made by company) was dissolved in 150.0 g of methyl ethyl ketone and heated to 70 ° C. To this solution, a solution prepared by dissolving 0.96 g of a polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 12.0 g of methyl ethyl ketone was dropped over 30 minutes. After completion of dropping, the reaction was further carried out at 70 ° C. for 4.5 hours. The reaction solution was allowed to cool and then added dropwise to 900.0 g of hexane, and the precipitated powder was collected by filtration and dried. In this way, 39.0 g of polymer B-7 was obtained. The weight average molecular weight of the obtained polymer was 39,200 in terms of standard polystyrene by GPC (Gel Permeation Chromatography) method, and the dispersity (Mw / Mn) was 3.7.

(Comparative Compound B)
The following compound RB-1 was used as Comparative Compound B.

<Synthesis of Compound RB-1>
25.0 g of 1H, 1H, 5H-octafluoropentyl methacrylate (Osaka Organic Chemical Co., Ltd., Viscoat 8FM) and 25.0 g of benzyl methacrylate (Osaka Organic Industry Co., Ltd.) were dissolved in 150.0 g of methyl ethyl ketone, This was heated to 70 ° C. To this solution, a solution prepared by dissolving 0.96 g of a polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) in 12.0 g of methyl ethyl ketone was dropped over 30 minutes. After completion of dropping, the reaction was further carried out at 70 ° C. for 4.5 hours. The reaction solution was allowed to cool and then added dropwise to 900.0 g of hexane, and the precipitated powder was collected by filtration and dried. In this way, 36.0 g of polymer B-7 was obtained. The weight average molecular weight of the obtained polymer was 24,100 in terms of standard polystyrene by GPC (Gel Permeation Chromatography) method, and the dispersity (Mw / Mn) was 3.0.

(Examples 1 to 21 and Comparative Examples 1 to 3)
Each component was added so that it might become a composition as described in the following table | surface, it stirred and it was made uniform and the curable composition was prepared.

(Other polymerizable compounds)
The following compounds were used as other polymerizable compounds.

<Non-conjugated vinylidene group-containing compound>
As the non-conjugated vinylidene group-containing compound, β-caryophyllene (manufactured by Inoue Fragrance Co., Ltd.) or (+)-limonene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. The optical isomer need not be particularly limited.

<Radical radical polymerization initiator>
Irgacure 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide: manufactured by BASF) was used as a radical photopolymerization initiator.

<Thermal radical polymerization initiator>
Perbutyl O (Nippon Yushi Co., Ltd .; t-butylperoxy-2-ethylhexanoate) and / or Parkmill H-80 (Nippon Yushi Co., Ltd .; cumene hydroperoxide) was used as a thermal radical polymerization initiator. .

(Evaluation)
<Abbe number and partial dispersion ratio>
The curable compositions obtained in the examples and comparative examples were poured into a transparent glass mold having a diameter of 10 mm and a thickness of 1 mm, and heated to 200 ° C. in an atmosphere having an oxygen concentration of 1% or less to prepare a thermoset. . The Abbe number (νd) and partial dispersion ratio (θg, F) of the obtained thermoset were measured using an Abbe refractometer (manufactured by Kalnew Optical Industry Co., Ltd.).
νd = (nd−1) / (nF−nC)
θg, F = (ng−nF) / (nF−nC)
Here, nd represents a refractive index at a wavelength of 587.56 nm, nF represents a refractive index at a wavelength of 486.13 nm, nC represents a refractive index at a wavelength of 656.27 nm, and ng represents a refractive index at a wavelength of 435.83 nm.
Next, Δ (θg, F) was calculated. Δ (θg, F) is a graph in which the Abbe number (νd) with respect to the d-line is the horizontal axis and the partial dispersion ratio (θg, F) is the vertical axis, glass type A (Ohara Corporation, glass type name NSL7) Is the difference between the partial dispersion ratio (θg, F) on the standard line and the partial dispersion ratio (θg, F) of the target object, where the straight line connecting the glass and glass type B (Ohara Corporation, glass type name PBM2) is the standard line .
In addition, although the thermosetting material was used for these measurements, even if it is the hardening material which performed the thermosetting after ultraviolet irradiation, there is no change in an Abbe number.

<Production of compound lens>
200 mg of the curable compositions obtained in the examples and comparative examples were injected into a molding die whose surface was treated with chromium nitride (the surface in contact with the curable composition had an aspherical shape). Transparent glass lens (glass material BK-7, diameter 33 mm, center thickness 3 mm, radius of curvature of the surface in contact with the curable composition = 44.3 mm, curable composition so as to cover all the surfaces on the side not in contact with the mold A convex lens having a radius of curvature of a surface not in contact with an object = 330.9 mm) was placed thereon, and the curable composition was spread so that the diameter of the curable composition was 30 mm. After this state, 300 mJ / cm ² of ultraviolet rays were irradiated from above the glass lens using Execute 3000 (manufactured by HOYA Corporation) (step of forming a semi-cured product). In addition, about the obtained semi-hardened | cured material, when the complex viscosity in 25 degreeC and the frequency of 10 Hz was measured using the rheometer RS6000 made from HAAKE, it was 5.0 * 10 < ⁶ > mPa * s. Next, while maintaining the state sandwiched between the molding die and the glass lens, the temperature was raised to 200 ° C. while applying a pressure of 0.196 MPa (2 kgf / cm ² ) to the curable composition and cured (cured). Forming a product). Then, after cooling the mold temperature to 180 ° C., a cured product of the curable composition and the molding mold were separated at a rate of 0.05 mm / second to produce a composite lens (step of separating the mold). . In order to use for the following evaluations, the above process was repeated 100 times to produce 100 compound lenses.

<Mold transferability>
The appearance of each compound lens produced as described above was evaluated using a digital microscope (trade name: VHX-1000) manufactured by Keyence Corporation. Those having fine irregularities (wrinkles) on the surface of the compound lens were determined to be defective, and those having no unevenness were determined to be non-defective. 100 manufactured composite lenses were evaluated, and the ratio of non-defective products was defined as the non-defective rate, and evaluated according to the following criteria. In addition, the rank 2 or higher was regarded as an acceptable level.
Rank 4: The yield rate was 90% or higher.
Rank 3: The yield rate was 70% or more and less than 90%.
Rank 2: The yield rate was 50% or more and less than 70%.
Rank 1: The yield rate was less than 50%.

In the cured product formed from the curable compositions obtained in the examples, the value of Δ (θg, F) was large and the mold transferability when molding the cured product was excellent.
On the other hand, in Comparative Example 1, since the compound A having no predetermined structure was used, the value of Δ (θg, F) was small. In Comparative Example 2, since compound B is not contained, the mold transferability is inferior. In Comparative Example 3, since compound B having no predetermined structure is used, it is formed from a curable composition. The cured product became cloudy and could not be evaluated.

Claims (9)

1. Compound A represented by the following general formula (A),
   Compound B having at least one fluorine atom and at least one radical crosslinkable group in one molecule;
   At least one selected from a thermal radical polymerization initiator and a photo radical polymerization initiator;
   A curable composition comprising:
   

   

   
   In general formula (A), Ar ¹¹ and Ar ¹² each independently represent an aryl group containing a benzene ring surrounded by a broken line or a heteroaryl group containing a benzene ring surrounded by a broken line as one of condensed rings;
   X ¹ , Y ¹ , X ² and Y ² are each independently an oxygen atom, a sulfur atom, a nitrogen atom or a carbon atom, and Z ¹ is a 5- to 7-membered aromatic ring together with X ¹ —C═C—Y ¹ Represents an atomic group that includes at least one selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a carbon atom, and Z ² represents 5 to 7 together with X ² —C═C—Y ² A group of atoms forming a member aromatic ring, the group of atoms including at least one selected from an oxygen atom, a sulfur atom, a nitrogen atom and a carbon atom;
   Ar ¹³ and Ar ¹⁴ each independently represent an arylene group containing an aromatic ring surrounded by a broken line or a heteroarylene group containing an aromatic ring surrounded by a broken line, and at least one of Ar ¹³ and Ar ¹⁴ is other than a phenylene group A group of
   R ³ to R ⁶ each independently represents a substituent, q and r are each independently an integer of 0 to 4, v is an integer of 0 or more, and the maximum number of v is X ¹ -C = The maximum number of substituents that can be substituted on the ring formed by CY ¹ and Z ¹ , w is an integer of 0 or more, and the maximum number of w is X ² -C = CY ² and Z ² is the maximum number of substituents that can be substituted on the ring formed;
   L ¹ and L ² each independently represents a single bond, an oxygen atom or a sulfur atom, and R ¹¹ and R ¹² each independently represent an ether bond, an ester bond, a thioether bond, a thioester bond, an amide bond, a carbonate bond and an alkylene. A linking group containing at least one selected from the group or a single bond, R ²¹ and R ²² each independently represents a hydrogen atom or a methyl group;
   When Ar ¹¹ to Ar ¹⁴ are each independently a condensed ring group containing an aromatic ring surrounded by a broken line as one of the condensed rings, a group having L ¹ as a linking group, a group having L ² as a linking group, and R ³ to R ⁶ may be each independently substituted with an aromatic ring surrounded by a broken line, or may be substituted with a condensed ring other than the aromatic ring surrounded by a broken line.
2. 2. The curable composition according to claim 1, wherein at least one of Ar ¹³ and Ar ¹⁴ is a condensed ring group containing an aromatic ring surrounded by a broken line.
3. The compound B is a compound having in a molecule at least one group selected from a fluoroalkyl group, a perfluoroalkyl group, a perfluoroalkylene group, and a perfluoroalkyleneoxy group and at least one radical crosslinkable group. The curable composition according to claim 1 or 2.
4. The curable composition according to any one of claims 1 to 3, further comprising a non-conjugated vinylidene group-containing compound.
5. A thermal radical polymerization initiator,
   The curable composition according to any one of claims 1 to 4, comprising a hydroperoxide compound as the thermal radical polymerization initiator.
6. A semi-cured product of the curable composition according to any one of claims 1 to 5, wherein the complex viscosity at 25 ° C and a frequency of 10 Hz is 10 ⁵ to 10 ⁸ mPa · s.
7. A cured product of the curable composition according to any one of claims 1 to 5.
8. An optical member comprising the cured product according to claim 7.
9. A lens comprising the cured product according to claim 7.