CN116940871A - Photochromic curable composition, photochromic laminate, and method for producing same - Google Patents

Photochromic curable composition, photochromic laminate, and method for producing same Download PDF

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Publication number
CN116940871A
CN116940871A CN202280020016.1A CN202280020016A CN116940871A CN 116940871 A CN116940871 A CN 116940871A CN 202280020016 A CN202280020016 A CN 202280020016A CN 116940871 A CN116940871 A CN 116940871A
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Prior art keywords
photochromic
component
group
curable composition
mass
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Inventor
花崎太一
宫崎真行
平连利光
森力宏
百田润二
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Tokuyama Corp
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Tokuyama Corp
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Priority claimed from PCT/JP2022/009857 external-priority patent/WO2022191160A1/en
Publication of CN116940871A publication Critical patent/CN116940871A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/02—Coumarine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Provided are a photochromic curable composition capable of providing a cured product having excellent appearance, a photochromic optical article comprising the cured product, and a method for producing the photochromic optical article. According to an embodiment, a photochromic curable composition can be provided that includes (a) a siloxane having an acyclic polysiloxane bond, and at least one of a radical polymerizable group and a group reactive with the radical polymerizable group; (B) a radically polymerizable monomer component; and (C) a photochromic compound.

Description

Photochromic curable composition, photochromic laminate, and method for producing same
Technical Field
The present invention relates to a photochromic curable composition, a photochromic laminate, and a method for producing the same.
Background
Photochromic compounds such as chromene compounds, fulgide compounds and spirooxazine compounds have photochromic properties, which are characteristics such that they rapidly change color when irradiated with light including ultraviolet rays such as sunlight or light from a mercury lamp, and they return to their original color when left in the dark after stopping the irradiation of light. Photochromic compounds are used for various applications, particularly for optical materials, by taking advantage of this property.
For example, photochromic glasses containing a photochromic compound are functional glasses that can be colored rapidly as sunglasses in the outdoors where sunlight is irradiated and can be discolored as colorless and transparent glasses in the indoors where no sunlight is irradiated. In recent years, demand for photochromic eyeglasses has increased.
Examples of the method for producing a photochromic optical article including the lens for photochromic glasses include a kneading method, an adhesive method, and a coating method (patent documents 1, 2, and 3). The kneading method is a method of forming a photochromic optical article such as a lens by polymerizing a polymerizable composition containing a polymerizable monomer and a photochromic compound. The pressure-sensitive adhesive method is a method of joining 1 pair of optical sheets by an adhesive layer containing a photochromic compound, and processing the resulting laminate into a lens or the like to obtain a photochromic optical article.
The coating method is a method having a high productivity as compared with the above-mentioned method. In the coating method, a curable composition containing a photochromic compound and a polymerizable monomer is first applied to the surface of a lens or the like by, for example, spin coating to form a coating film. The coating film was cured to obtain a laminate having a photochromic resin layer on the surface of the lens. The laminate can be used as a photochromic optical article. In the coating method, a leveling agent may be blended in the curable composition in order to make the surface of the coating film uniform.
In the photochromic optical article such as a photochromic lens obtained by the above coating method, a protective film may be attached to the surface of the photochromic resin layer. That is, in the process of manufacturing an optical device such as a photochromic sunglass using a photochromic lens as a component, and during storage and shipment of the manufactured optical device, the photochromic resin layer of the lens may be scratched or dust may adhere thereto. By covering the surface of the photochromic resin layer of the lens with a protective film, such scratch and dust adhesion can be prevented. In addition, as the protective film, a colored film may be used. The photochromic lens is colorless and transparent when no ultraviolet light is irradiated, and therefore, the colored protective film attached to the surface thereof can function as an identification tag. As the protective film, for example, a general-purpose protective film using an acrylic adhesive on the adhesive surface is used.
Prior art literature
Patent literature
Patent document 1: international publication No. 2012/176839
Patent document 2: international publication No. 2013/099640
Patent document 3: international publication No. 2015/068798
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide that: a photochromic curable composition which can provide a cured product having excellent appearance, a photochromic optical article comprising the cured product, and a method for producing the photochromic optical article.
Solution for solving the problem
A first embodiment is a photochromic curable composition comprising:
(A) A siloxane having an acyclic polysiloxane bond, and at least one of a radical polymerizable group and a group reactive with the radical polymerizable group;
(B) A radically polymerizable monomer component; and
(C) Photochromic compounds.
In addition, the first embodiment preferably adopts the following scheme.
The amount of the siloxane is preferably 0.01 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the radical polymerizable monomer component.
The siloxane preferably contains a compound represented by the following formula (8).
In the formula (8), n is a number of 0 to 20. o is a number from 0 to 20. p is a number of 0 to 20.
R 18 、R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 、R 28 R is R 29 Respectively hydrogen atom, alkyl group with 1-20 carbon atoms, alkoxy group with 1-20 carbon atoms, phenyl group, - (CH) 2 ) α OR 30 、-(CH 2 CH 2 O) α R 30 、-(CH(CH 3 )CH 2 O) α R 30 、-(CH 2 CH(CH 3 )O) α R 30 、-(CH 2 ) q O-(CH 2 CH 2 O) r R 30 -、-(CH 2 ) q O-(CH(CH 3 )CH 2 O) r R 30 、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r R 30 、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r R 30 、-(CH 2 CH(CH 3 )O) q -(CH 2 CH 2 O) r R 30 、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s R 30 、-(CH 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s R 30 、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s R 30 、-(CH 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s -(CH 2 CH 2 O) z R 30 Acryl, methacryl, vinyl, thiol, amino, -R 31 NH 2 An epoxy group, a group represented by the following formula (9), or a group represented by the following formula (10).
R 30 Is hydrogen atom, methyl, ethyl, n-propyl or isopropyl.
R 31 Is alkylene or- (CH) having 1 to 20 carbon atoms 2 ) α O-。
Wherein R is 18 ～R 29 At least one of them is an acryl, methacryl, vinyl, thiol, amino, -R 31 NH 2 An epoxy group, a group represented by the following formula (9), or a group represented by the following formula (10).
In the formula (9), R 32 Is an alkylene group having 1 to 20 carbon atoms, - (CH) 2 ) α O-、-(CH 2 CH 2 O) α -or- (CH) 2 CH(CH 3 )O)α-。R 33 Is a hydrogen atom or a methyl group.
In the formula (10), R 34 Is an oxygen atom, - (CH) 2 ) α O-、-(CH 2 CH 2 O) α- 、-(CH(CH 3 )CH 2 O) α -、-(CH 2 CH(CH 3 )O)α-、-(CH 2 ) q O-(CH 2 CH 2 O) r -、-(CH 2 ) q O-(CH(CH 3 )CH 2 O) r -、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r -、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r -、-(CH 2 CH(CH 3 )O) q -(CH 2 CH 2 O) r -、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s -、-(CH 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s -、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s -or- (CH) 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s -(CH 2 CH 2 O) z -。
R 35 Is a hydrogen atom or a methyl group.
In the formulas (8), (9) and (10), α is a number of 1 to 20, and q, r, s and z are each a number of 0 to 20. q+r is a number of 1 to 40. q+r+s is a number of 1 to 60. q+r+s+z is a number of 1 to 80.
The radical polymerizable group of the siloxane and the group reactive with the radical polymerizable group preferably contain a (meth) acryloyl group.
The radically polymerizable monomer component preferably contains a polyrotaxane compound having a radically polymerizable group.
The radically polymerizable monomer component preferably contains silsesquioxane having a (meth) acryloyl group of 2 or more functions.
It is preferable that the reactive hindered amine compound further comprises 1 or more reactive groups selected from at least 1 of the group consisting of radical polymerizable groups and groups reactive with the radical polymerizable groups.
The non-reactive hindered amine compound further comprising a group that does not have a radical polymerizable group and a group that reacts with the radical polymerizable group is preferred.
Preferably, the composition further comprises an organic compound having a boiling point of 80 ℃ to 200 ℃ inclusive and an SP value of 8.0 to 10.0 inclusive.
A second embodiment is a photochromic stack comprising:
an optical substrate,
A photochromic resin layer which is a cured product of the curable composition according to the first embodiment, and a polyurethane resin layer which is located between the optical substrate and the photochromic resin layer.
A third embodiment is a method for manufacturing a photochromic laminate, comprising:
a step of forming a polyurethane resin layer by applying a coating liquid containing at least 1 compound selected from the group consisting of polyurethane resins and precursors of moisture-curable urethane resins, and a solvent having a boiling point of 70 ℃ or higher and an SP value of 8.0 or higher, on one surface of an optical substrate and removing the solvent from the coating film; and
and a step of forming a photochromic resin layer by applying the photochromic curable composition of the first embodiment to the urethane resin layer and curing the coating film.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide: a photochromic curable composition which can provide a cured product having excellent appearance, a photochromic optical article comprising the cured product, and a method for producing the photochromic optical article.
Drawings
Fig. 1 is a schematic diagram showing an example of a molecular structure of polyrotaxane.
Detailed Description
The photochromic curable composition of the embodiment comprises the following components (A), (B) and (C).
(A) A siloxane having an acyclic polysiloxane bond and at least one of a radical polymerizable group and a group reactive with the radical polymerizable group
(B) Radical polymerizable monomer component
(C) Photochromic compounds
When the photochromic curable composition according to the embodiment is used, a cured product having high uniformity and excellent appearance can be obtained, in which the occurrence of fine lines or the like in the form of wrinkles can be suppressed. Thus, a photochromic optical article excellent in appearance can be obtained. For this reason, the present inventors consider the following.
First, when the protective film is adhered to the photochromic resin layer, a desired color tone of the photochromic optical article may not be obtained, and appearance defects such as wrinkles may occur. That is, in the photochromic optical article from which the protective film is removed, the adhesive and the colorant contained in the protective film may adhere to the surface of the photochromic resin layer. If the binder and the colorant remain or penetrate the surface of the photochromic resin layer, the color tone of the photochromic resin layer may deviate from the desired color tone. In addition, fine lines like wrinkles may sometimes enter the inside of the photochromic resin layer.
The present inventors have found that the fine line shaped like wrinkles is caused by an adhesive applied to the adhesive surface of the protective film. That is, it is considered that the acrylic adhesive used for the protective film penetrates from the adhesive surface of the protective film into the inside of the photochromic resin layer and is cured in the inside of the photochromic resin layer, thereby appearing as lines or stripes.
The present inventors have further studied intensively, and as a result, have found that the penetration of the acrylic adhesive is affected by a leveling agent. That is, as the leveling agent in the curable composition, a non-reactive silicone oil or the like is generally used. The non-reactive silicone oil is a siloxane of the following structure: has a linear polysiloxane skeleton, and the terminal or side chain of the polysiloxane skeleton is modified with a non-reactive organic functional group. The leveling agent is oriented on the surface of the coating film to reduce the surface tension of the coating film surface. This makes it possible to smooth the surface of the coating film by removing irregularities while suppressing an increase in the viscosity of the curable composition. It is considered that the leveling agent is cured in a state of being oriented on the surface of the coating film, and thus is also oriented on the surface of the photochromic resin layer. It is seen that the leveling agent tends to easily enter the inside of the photochromic resin layer when components such as an adhesive of the protective film are oriented on the surface of the resin layer. Therefore, it is considered that when the conventional leveling agent is used, on the one hand, the smoothness of the coating film is improved, and on the other hand, fine lines or streaky foreign matter derived from the protective film are observed in the photochromic resin layer.
When a curable composition containing no conventional leveling agent is used, a photochromic resin layer containing no fine lines like wrinkles can be obtained. On the other hand, in the photochromic resin layer obtained from such a curable composition, the film thickness may become uneven, and a plurality of irregularities may appear on the surface, thereby giving a so-called orange-peel appearance. In addition, when the curable composition is applied by spin coating, spiral marks may be seen in the photochromic resin layer due to the non-uniformity of the coating film.
The photochromic curable composition of the embodiment comprises: (A) A siloxane having an acyclic polysiloxane bond, and at least one of a radical polymerizable group and a group reactive with the radical polymerizable group; and (B) a radically polymerizable monomer component. Hereinafter, at least one of the radical polymerizable group and the group reactive with the radical polymerizable group is also referred to as a radical reactive group. The component (a) functions as a leveling agent because it has an acyclic polysiloxane bond and a radical reactive group. (A) The radical reactive group of the component (c) reacts with the component (B) when the curable composition is cured. In the cured product of the composition, at least a part of the component (a) and the component (B) is considered to be in the form of a polymerized composite. It is considered that the orientation of the component (a) and the component (B) in such a composite decreases on the surface of the photochromic resin layer because the component (a) and the component (B) polymerize. That is, in the coating film of the photochromic curable composition, the component (a) can be oriented on the surface of the coating film in the same manner as the conventional leveling agent, and the surface tension thereof can be reduced. Thus, when the photochromic curable composition according to the embodiment is used, a coating film having high uniformity can be obtained. Further, it is considered that when the coating film is cured, the component (a) and the component (B) polymerize to form a complex, and thus the orientation of the surface is suppressed, and the random dispersibility in the photochromic resin layer is improved. Thus, a photochromic resin layer which is less susceptible to the adhesive and colorant contained in the protective film attached to the surface can be obtained. Based on the above, when the photochromic curable composition according to the embodiment is used, a photochromic resin layer having excellent appearance, such as a fine line which has high uniformity and is less likely to generate wrinkles, can be formed.
The components contained in the curable composition will be described in detail below.
Component (A)
(A) The component (a) is a siloxane having acyclic polysiloxane bonds and free radical reactive groups. As described above, the component (a) functions as a leveling agent.
The radical polymerizable group of the component (a) includes at least 1 functional group selected from the group consisting of an acryl group, a methacryl group, and a vinyl group. The functional group containing at least one of an acryl group and a methacryl group may be referred to as a (meth) acryl group. The group reactive with the radical polymerizable group includes at least 1 functional group selected from the group consisting of a thiol group, an amino group, and an epoxy group. These reactive groups are groups capable of polymerizing or reacting with the component (B) described in detail below. Particularly preferred is a (meth) acryl group. (A) The component (a) may have, as the radical-reactive group, both a radical-polymerizable group and a group reactive with the radical-polymerizable group, or may have one of them. (A) The component (B) preferably has a radical polymerizable group of the same kind as the radical polymerizable group of the component (B). By making the radically polymerizable group of the component (a) and the radically polymerizable group of the component (B) be similar functional groups, the reactivity of the component (a) and the component (B) is further improved, and a cured product excellent in appearance can be obtained. Here, acryl and methacryl can be considered as the same kind of functional group. As the component (a), at least one of silicone polyether acrylate and silicone acrylate is preferably used.
(A) The components are chemically bonded in the matrix of the photochromic resin layer. In the photochromic resin layer, the component (a) is present in a form of being bonded to the matrix, so that the component (a) can be inhibited from being oriented on the surface, the stability of the photochromic optical article can be maintained highly, and the photochromic optical article having a good appearance can be obtained.
(A) The component (a) is not particularly limited as long as it is a siloxane having an acyclic polysiloxane bond and a radical polymerizable group. (A) The component (a) may contain a functional group which is not reactive, in addition to the radical reactive group. Examples of such a non-reactive functional group include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 4 to 10 carbon atoms, and a polymer group having 2 to 20 carbon atoms. Specific examples of the polymer group having 2 to 20 carbon atoms include polypropylene group, polyether group, polyethylene group, polyolefin group and the like. (A) The component (c) may contain a plurality of the above-mentioned non-reactive functional groups, and preferably contains at least 1 functional group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a polymer group having 2 to 20 carbon atoms. More preferably, the non-reactive functional group is at least 1 selected from the group consisting of methyl, methoxy, ethoxy, phenyl, polypropylene and polyether groups.
Among them, the compound represented by the following formula (8) is preferable. Hereinafter, the component (A8) may be referred to simply as "component".
In the formula (8), n is a number of 0 to 20, preferably a number of 1 to 15. o is a number of 0 to 20, preferably a number of 1 to 15. p is a number of 0 to 20, preferably a number of 1 to 15.
R 18 、R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 、R 28 R is R 29 Respectively are provided withIs hydrogen atom, alkyl group with 1-20 carbon atoms, alkoxy group with 1-20 carbon atoms, phenyl group, - (CH) 2 ) α OR 30 、-(CH 2 CH 2 O) α R 30 、-(CH(CH 3 )CH 2 O) α R 30 、-(CH 2 CH(CH 3 )O) α R 30 、-(CH 2 ) q O-(CH 2 CH 2 O) r R 30 -、-(CH 2 ) q O-(CH(CH 3 )CH 2 O) r R 30 、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r R 30 、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r R 30 、-(CH 2 CH(CH 3 )O) q -(CH 2 CH 2 O) r R 30 、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s R 30 、-(CH 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s R 30 、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s R 30 、-(CH 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s -(CH 2 CH 2 O) z R 30 Acryl, methacryl, vinyl, thiol, amino, -R 31 NH 2 An epoxy group, a group represented by the following formula (9), or a group represented by the following formula (10).
As the alkyl group having 1 to 20 carbon atoms, methyl or ethyl is preferable. The alkoxy group having 1 to 20 carbon atoms is preferably methoxy or ethoxy.
R 30 Is hydrogen atom, methyl, ethyl, n-propyl or isopropyl.
R 31 Is alkylene or- (CH) having 1 to 20 carbon atoms 2 ) α O-。
Wherein R is 18 ～R 29 At least one of them is an acryl, methacryl, vinyl, thiol, amino, -R 31 NH 2 An epoxy group, a group represented by the following formula (9), or a group represented by the following formula (10).
In the formula (9), R 32 Is an alkylene group having 1 to 20 carbon atoms, - (CH) 2 ) α O-、-(CH 2 CH 2 O) α -or- (CH) 2 CH(CH 3 )O) α -。R 32 Si is bonded to any one of the above formulas (8).
R 33 Is a hydrogen atom or a methyl group.
In the formula (10), R 34 Is an oxygen atom, - (CH) 2 ) α O-、-(CH 2 CH 2 O) α -、-(CH(CH 3 )CH 2 O) α -、-(CH 2 CH(CH 3 )O) α -、-(CH 2 ) q O-(CH 2 CH 2 O) r -、-(CH 2 ) q O-(CH(CH 3 )CH 2 O) r -、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r -、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r -、-(CH 2 CH(CH 3 )O) q -(CH 2 CH 2 O) r -、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s -、-(CH 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s -、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s -or- (CH) 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s -(CH 2 CH 2 O) z -。R 34 Is bonded to any one of Si in the above formula (8).
R 35 Is a hydrogen atom or a methyl group.
In the formulae (8), (9) and (10), α is a number of 1 to 20, preferably a number of 1 to 15. q, r, s and z are each a number from 0 to 20. q+r is a number of 1 to 40. q+r+s is a number of 1 to 60. q+r+s+z is a number of 1 to 80.
The radical polymerizable group of the siloxane and the group reactive with the radical polymerizable group preferably contain a (meth) acryloyl group.
(A8) The structure of the component and the kind of the functional group can be determined by, for example 1 H-NMR analysis, infrared absorption spectrum (IR) analysis, and liquid chromatography-mass spectrometry (LC-MS) analysis).
As the component (A8), commercially available products can be used.
Examples of the (A8) component having at least 1 functional group selected from the group represented by formula (9), the group represented by formula (10), and the acryl group include, for example, TEGO (registered trademark) RAD2100, TEGO (registered trademark) RAD2300, BYK Japan KK BYK (registered trademark) -UV3505, BYK (registered trademark) -UV3510, BYK (registered trademark) -UV3530, BYK (registered trademark) -3550, BYK (registered trademark) -3560, BYK (registered trademark) -UV3565, BYK (registered trademark) -3566, BYK (registered trademark) -UV3500, BYK (registered trademark) -UV3535, BYK (registered trademark) -UV3570, BYK (registered trademark) -UV3575, BYK (registered trademark) -UV3576, and BYK-24513, and KR-45, by the company, and the like.
Examples of the component (A8) having a methacryloyl group include X-40-9296, X-22-164-A, X-22-164B, X-22-164C, X-22-164E, which are manufactured by Kagaku Kogyo Co., ltd.
As the vinyl group-containing (A8) component, KR-511, available from Kagaku Kogyo Co., ltd, for example, may be mentioned.
Examples of the component (A8) having an amino group include KF-8010, KF-8012, X-22-161A, X-22-161B, KF-8008, DOw Toray Co., ltd., DOWSIL (registered trademark) BY16-205, DOWSIL (registered trademark) BY16-213, DOWSIL (registered trademark) 16-849Fluid, DOWSIL (registered trademark) 16-853U, DOWSIL (registered trademark) 16-871, DOWSIL (registered trademark) 16-879B, DOWSIL (registered trademark) 16-892, DOWSIL (registered trademark) FZ-3705, DOWSIL (registered trademark) FZ-3710Fluid, DOWSIL (registered trademark) FZ-3785, DOWSIL (registered trademark) SF-8417Fluid, and the like.
Examples of the thiol (mercapto) group-containing component (A8) include KR-518, X-22-167B, X-22-167C, X-22-173BX, and X-22-173DX, all manufactured by Kagaku chemical Co., ltd.
Examples of the component (A8) having an epoxy group include KR-516, KR-517, X-24-9590, X-41-1590A, dow Toray Co., ltd., DOWSIL (registered trademark) BY16-839, DOWSIL (registered trademark) BY16-876, DOWSIL (registered trademark) FZ-3736Fluid, DOWSIL (registered trademark) SF8411Fluid, DOWSIL (registered trademark) SF8413Fluid, DOWSIL (registered trademark) SF8421Fluid, DOWSIL (registered trademark) L-9300, and the like.
(A) Preferred compounding ratio of the ingredients
(A) The compounding amount of the components is not particularly limited. (A) The amount of the component (A) is preferably 0.01 to 10.0 parts by mass based on 100 parts by mass of the component (B). (A) If the component is too much or too little, the coating film of the curable composition may have reduced smoothness, and a plurality of irregularities may be formed on the cured product, which may reduce the appearance. Further, in order to improve the smoothness of the curable composition and to improve the appearance of the cured product, the amount of the component (a) is more preferably 0.05 parts by mass or more and 5.0 parts by mass or less, and still more preferably 0.10 parts by mass or more and 2.0 parts by mass or less.
(A) The compounding amount of the components can be confirmed by the following method, for example. When the amount of the component (a) is calculated from the cured product or curable composition as the photochromic resin layer, the cured product or curable composition is first dissolved in an organic solvent to obtain a sample. Purifying the sample by gel filtration column chromatography, etc., separatingA) The components are as follows. For the isolated component (A), the method comprises the following steps of 1 H-NMR analysis, liquid chromatography-mass spectrometry (LC-MS) analysis, infrared absorption spectrum (IR) analysis, and gas chromatography-mass spectrometry (GC-MS) analysis, the structure of component (A) is determined, and the content is calculated.
When 1 type of component (B) is used, the amount of component (B) is set to 100 parts by mass. However, as will be described below, the component (B) may contain a plurality of radically polymerizable monomers. When a plurality of radical polymerizable monomers are used as the component (B), the total amount of these plurality of radical polymerizable monomers is set to 100 parts by mass.
Component (B)
(B) The component (c) may be the main component of the curable composition of the embodiment. In the cured product obtained from the curable composition, the component (B) may be a main component of the matrix. The component (B) is a radical polymerizable monomer. As the radical polymerizable monomer, a monomer having at least 1 radical polymerizable group selected from the group consisting of an acryl group, a methacryl group, and a vinyl group can be used.
(B) The component (c) preferably contains a polyfunctional (meth) acrylate having 2 or more (meth) acryloyl groups in the molecule. Among them, a polyrotaxane having a (meth) acryloyl group and having a weight average molecular weight of 100000 to 1000000 is preferably contained. Hereinafter, this polyrotaxane is also referred to as a component (B1). The component (B) preferably contains a silsesquioxane having a radical polymerizable group and having a weight average molecular weight of 1500 or more and 20000 or less. Hereinafter, this silsesquioxane is also referred to as a (B2) component. The component (B) more preferably contains both the component (B1) and the component (B2). When a curable composition containing at least one of the component (B1) and the component (B2) is used, a cured product having excellent mechanical properties and photochromic properties can be obtained.
(B1) Composition of the components
(B1) The components are known compounds and have the structure shown in fig. 1. Fig. 1 is a schematic diagram showing an example of a molecular structure of polyrotaxane. The polyrotaxane 1 shown in fig. 1 has a plurality of cyclic molecules 3, an axial molecule 2 penetrating the inner side of the ring of the plurality of cyclic molecules 3, a bulky terminal group 4 modifying the terminal end of the axial molecule 2, and a side chain 5 bonded to the plurality of cyclic molecules 3. Although one cyclic molecule 3 has a plurality of side chains 5 in fig. 1, the number of side chains 5 bonded to the cyclic molecule 3 may be only 1. (B1) The composition has a structure as shown in fig. 1, and thus the flexibility of the matrix of the cured product can be improved. Therefore, when the component (B1) is used, the structural change of the photochromic compound in the cured product is not easily inhibited, and the photochromic property of the cured product tends to be improved.
Various kinds of shaft molecules are known as the shaft molecule 2, and for example, the shaft molecule 2 may be linear or branched within a range capable of penetrating the ring of the cyclic molecule 3, and is usually formed of a polymer.
(B1) Among the components, preferred as the polymer forming the axial molecule are polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol or polyvinyl methyl ether, and most preferred is polyethylene glycol.
The groups formed at both ends of the shaft molecule are not particularly limited as long as they are groups for preventing the cyclic molecule from being detached from the shaft molecule, but are preferably bulky groups (bulky terminal groups 4 in fig. 1), and examples thereof include adamantyl groups, trityl groups, fluorescein groups, dinitrophenyl groups, and pyrenyl groups, and in particular, adamantyl groups are preferable from the viewpoint of easy introduction.
The molecular weight of the axial molecule is not particularly limited, but if it is too large, compatibility with other components such as other polymerizable monomers tends to be poor, and if it is too small, fluidity of the cyclic molecule tends to be low and photochromic tends to be low. From this viewpoint, the weight average molecular weight Mw of the axial molecule is preferably in the range of 1000 to 100000, particularly 5000 to 80000, and particularly preferably 8000 to 30000. The weight average molecular weight Mw is a value measured by a GPC measurement method described in examples described later.
The cyclic molecule may have a ring having a size capable of binding the above-mentioned axial molecule, and examples of such a cyclic molecule include cyclodextrin ring, crown ether ring, benzocrown ring, dibenzocrown ring and dicyclohexyl crown ring, and cyclodextrin ring is particularly preferable. The cyclodextrin ring includes an α -form (ring inner diameter 0.45 to 0.6 nm), a β -form (ring inner diameter 0.6 to 0.8 nm), and a γ -form (ring inner diameter 0.8 to 0.95 nm), and particularly preferably an α -cyclodextrin ring and a γ -cyclodextrin ring, and most preferably an α -cyclodextrin ring.
The number of cyclic molecules having the above-mentioned rings is preferably in the range of 0.001 to 0.6, more preferably 0.002 to 0.5, and even more preferably 0.003 to 0.4, when the maximum number of cyclic molecules that can be bonded per 1 axial molecule is generally 1. If the number of cyclic molecules included is too large, the cyclic molecules are densely present with respect to 1 axis molecule, and thus the fluidity tends to be low, and the photochromic property of the cured product tends to be low. In addition, when the number of the inclusions is too small, gaps between the axial molecules are narrowed, flexibility allowing reversible reaction of the photochromic compound molecules is reduced, and the photochromic property of the cured product tends to be lowered.
As the component (B1), polyrotaxane in which radical polymerizable groups are introduced into the side chains 5 of the plurality of cyclic molecules 3 in fig. 1 is used. Such a component (B1) can be obtained, for example, by modifying a polyrotaxane having a hydroxyl group at the end of the side chain 5 by a known method.
The side chain having a hydroxyl group at the terminal is not particularly limited, but a side chain formed by repetition of an organic chain having a hydroxyl group at the terminal and having a long chain carbon number in the range of 3 to 20 is preferably used. The average molecular weight of such side chains is preferably in the range of 300 to 10000, preferably 350 to 8000, more preferably 350 to 5000, most preferably 400 to 1500. The average molecular weight of the side chain can be adjusted by the amount used in introducing the side chain and can be calculated from the calculation 1 H-NMR measurement can also be performed.
The side chain having a hydroxyl group at the terminal as described above may be introduced by modifying a functional group of a cyclic molecule. For example, an α -cyclodextrin ring has 18 hydroxyl groups as functional groups, and side chains are introduced through the hydroxyl groups. That is, for 1 α -cyclodextrin ring, a maximum of 18 side chains can be introduced. In order to fully exert the functions of the side chains, it is preferable that 6% or more, particularly 30% or more of the total functional groups of such a ring be modified with side chains. The functional group of the cyclic molecule may affect the compatibility with other components, and particularly when the functional group is a hydroxyl group, the compatibility with other components may be greatly affected. Therefore, the ratio (degree of modification) of the functional group to be modified is preferably 6% or more and 80% or less, more preferably 30% or more and 70% or less.
The side chain having a hydroxyl group at the terminal as described above may be linear or branched as long as the terminal has a hydroxyl group. In addition, by using ring-opening polymerization; free radical polymerization; cationic polymerization; anionic polymerization; the desired side chain can be formed by introducing a side chain to the functional group of the cyclic molecule such that the terminal has a hydroxyl group, for example, living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, NMP polymerization, or the like.
For example, a side chain derived from a cyclic compound such as a lactone or a cyclic ether can be introduced by ring-opening polymerization. The side chain introduced by ring-opening polymerization of a cyclic compound such as a lactone or a cyclic ether has a hydroxyl group introduced at the terminal of the side chain.
Among the cyclic compounds, from the viewpoints of easy availability, high reactivity and easy adjustment of size (molecular weight), cyclic ethers and lactone compounds are preferably used, and among the lactone compounds preferably used, epsilon-caprolactone is preferred.
In addition, when a side chain is introduced by reacting a cyclic compound by ring opening polymerization, there is a case where the reactivity of a functional group (for example, a hydroxyl group) bonded to a ring is insufficient, and particularly it is difficult to directly react a large molecule due to steric hindrance or the like. In this case, for example, the following means may be employed for reacting caprolactone or the like: a low molecular compound such as propylene oxide is reacted with a functional group to undergo hydroxypropylation, and a functional group (for example, a hydroxyl group) having high reactivity is introduced into the terminal, and then ring-opening polymerization is performed using the cyclic compound described above, whereby a side chain is introduced. In this case, the hydroxypropylated moiety can also be regarded as a side chain.
(B1) In the component (A), a hydroxyl group at the end of a side chain of polyrotaxane is reacted with a compound having a radical polymerizable group, whereby a polymerizable group is introduced into the end of the side chain of polyrotaxane. This reaction is referred to as "modification".
The compound having a radical polymerizable group is introduced by using a side chain having a hydroxyl group at the end, and a compound which reacts with the hydroxyl group of the side chain can be used appropriately. In view of compatibility with other components, the compound having a radical polymerizable group is preferably a compound having no hydroxyl group in the molecule. The radical polymerizable group is preferably a (meth) acryl group.
The compound having a radical polymerizable group is a compound having 2 groups, i.e., a functional group capable of reacting with a hydroxyl group of a side chain and a polymerizable group, in 1 molecule. Examples of the functional group capable of reacting with a hydroxyl group include an isocyanate group, a carboxyl group, and an acid chloride group (e.g., —cocl group). By reacting a compound having an isocyanate group, a radical polymerizable group is introduced through a urethane bond. Or by reacting a compound having a carboxyl group, an acid chloride group, or the like, a radical polymerizable group is introduced through an ester bond.
The reaction of the compound having a radically polymerizable group with the hydroxyl group of the side chain may be carried out under known reaction conditions of a functional group reactive with the hydroxyl group.
(B1) In the component (a), the ratio of the modification of the hydroxyl groups at the terminal of the side chain, that is, the ratio of the reaction of the compound having a radically polymerizable group to the number of moles of all the hydroxyl groups of the side chain is preferably 1 mol% or more and less than 100 mol%, and from the viewpoints of yield, mechanical strength, photochromic properties, etc., of the obtained cured product, the ratio of the modification of the compound having a radically polymerizable group is more preferably 10 mol% or more and 95 mol% or less, further preferably 30 mol% or more and 95 mol% or less, and from the viewpoints of productivity of the polyrotaxane compound itself, particularly preferably 70 mol% or more and 95 mol% or less.
The modification ratio can be calculated by (the number of moles of the polymerizable group introduced)/(the number of moles of all hydroxyl groups in the side chain) ×100. In the following, the component (B2) may be modified with a compound having no radical polymerizable group. Therefore, the remaining hydroxyl groups in the side chains may also be modified with a compound having no radical polymerizable group as described in detail below. However, in this case, the modification ratio is high, and therefore, a hydroxyl group may remain.
(B1) In the component (a), it is necessary to modify the hydroxyl group at the end of the side chain introduced into the cyclic molecule with a compound having a radical polymerizable group. The remaining hydroxyl groups of the side chain (that is, hydroxyl groups of the hydroxyl groups at the end of the side chain introduced into the cyclic molecule, which are not modified with a compound having a radical polymerizable group) may be modified with a compound having no radical polymerizable group while maintaining the hydroxyl group state.
The compound having no radical polymerizable group is a compound having a functional group reactive with a hydroxyl group of a side chain in 1 molecule, and the radical polymerizable group is not contained in the molecule. Therefore, the compound having no radical polymerizable group preferably has an alkyl group having 2 to 20 carbon atoms, an alkyleneoxy group having 2 to 30 carbon atoms, or an aryl group having 6 to 20 carbon atoms instead of the radical polymerizable group. The functional group that can react with the hydroxyl group of the side chain may be the same as the functional group described in "compound having a radically polymerizable group".
As the compound having an isocyanate group, an isocyanate compound having 2 to 20 carbon atoms (excluding carbon atoms of the isocyanate group) is preferable from the viewpoints of easiness in raw material acquisition and high reactivity with a hydroxyl group. As the carboxylic acid chloride, a carboxylic acid chloride having 2 to 20 carbon atoms (excluding the carbon atom of the carbonyl group) is preferable from the viewpoints of easiness in raw material acquisition and high reactivity with a hydroxyl group.
The modification ratio of the compound having no radical polymerizable group can be calculated from (the number of moles of the compound having no radical polymerizable group introduced)/(the number of moles of all hydroxyl groups of the side chain) ×100. The modification ratio is not particularly limited. Among them, the modification ratio based on the compound having no radical polymerizable group is preferably 0 to 99 mol%, more preferably 5 to 90 mol%, further preferably 5 to 70 mol%, particularly preferably 5 to 30 mol%, in view of the yield, mechanical strength, photochromic property, and the like of the obtained cured product.
Preferred structure and molecular weight of component (B1)
Among the above components, component (B1) preferably used is a cyclic molecule having an α -cyclodextrin ring formed by using polyethylene glycol having adamantyl groups bonded to both ends as an axial molecule, and a side chain having a (meth) acryloyl group at the terminal is introduced into the cyclic molecule by polycaprolactone.
The weight average molecular weight Mw of the component (B1) is preferably within the range of 100000 ～ 1000,000. When the weight average molecular weight Mw of the component (B1) is within this range, compatibility with other components is improved, and transparency of the cured product can be further improved. The weight average molecular weight Mw of the component (B1) is more preferably within the range of 100000 ～ 800000, and still more preferably within the range of 100000 ～ 500000, in view of compatibility with other components, transparency of the cured product, and the like. The weight average molecular weight Mw is a value measured by the GPC measurement method described in examples below.
Particularly preferred components (B1) are as follows. The molecular weight of the shaft molecule is preferably 8000 to 30000, the ratio of the introduced α -cyclodextrin ring is preferably 0.003 to 0.4, and the ratio of the modified α -cyclodextrin ring (degree of modification) is preferably 30% to 70%. The α -cyclodextrin ring preferably has a side chain having a molecular weight in the range of 400 to 1,500 on the average, and the modification ratio of the side chain based on the (meth) acryloyl group is 70 mol% or more and 95 mol% or less. Based on these values, the number of (meth) acryloyl groups per 1 molecule of the component (B1) is preferably 10 to 1000.
(B1) Compounding amount of the ingredients
The amount of the component (B1) is preferably 0 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the component (B).
(B2) Composition of the components
(B2) The component (C) is a radically polymerizable monomer having silicon in the molecule and a (meth) acryloyl group having a functionality of 2 or more. As the component (B2), 1-structure silsesquioxane may be used, or a mixture of various-structure silsesquioxanes may be used. Silsesquioxane has a cage-like, ladder-like or random molecular structure. Since the component (B2) has a cyclic siloxane structure, the surface tension of the curable composition can be reduced. Therefore, when the curable composition containing the component (B2) is used, the smoothness of the coating film of the curable composition tends to be improved, and a cured product having more excellent appearance tends to be obtained.
As the component (B2), a silsesquioxane having a (meth) acryloyl group with a weight average molecular weight of 1500 or more and 20000 or less is preferably used.
As the component (B2), a substance represented by the following formula (6) is preferably used.
(R 15 -SiO 3/2 ) k (6)
(wherein k is an integer of 3 to 100, and R is plural 15 And may be the same or different from each other, and is an organic group containing at least 2 or more (meth) acryloyl groups. Wherein R is 15 Does not contain a chain organosiloxane group-containing group. )
Here, R is 15 The (meth) acryl-containing organic group in (a) includes the case of only (meth) acryl (including the case where a silicon atom is directly bonded to a (meth) acryl group). Specifically, the (meth) acryl group may include not only a (meth) acryl group but also a (meth) acryloxypropyl group and a (3- (meth) acryloxypropyl) dimethylsilyloxy group. Among them, the (meth) acryloxypropyl group is particularly preferable because it is easy to obtain a raw material at the time of producing the component (B2), and it is possible to obtain a high film strength while exhibiting excellent photochromic characteristics.
(B2) The weight average molecular weight Mw of the component (A) is preferably 1500 to 20000, and the (meth) acrylic acid equivalent is preferably 150 to 800. The weight average molecular weight Mw of the component (B2) is a value measured by Gel Permeation Chromatography (GPC).
The component (B2) preferably contains 10 or more (meth) acryloyl groups in the average 1 molecule, and among these, 10 to 100 (meth) acryloyl groups in the average 1 molecule are preferable, and 15 to 35 are more preferable.
The method for synthesizing the component (B2) may be, for example, a method described in the cited document (see appl. Organic metal. Chem.2001, p.683-692) or a method described in the patent document (Japanese patent application laid-open No. 2004-143449 and Japanese patent application laid-open No. 1999-29640).
(B2) Compounding amount of the ingredients
The amount of the component (B2) is preferably 0 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and still more preferably 0.1 to 6 parts by mass, based on 100 parts by mass of the component (B).
(B3) Composition of the components
(B) The component (B3) is preferably contained as another radical polymerizable monomer in addition to the component (B1) and the component (B2). (B3) The radical polymerizable group of the component is preferably a (meth) acryloyl group. The following 3 types of acrylic acid esters are examples of the component (B3).
A 2-functional (meth) acrylate having 2 (meth) acryloyl groups in the molecule (hereinafter also referred to simply as a (B31) component),
Multifunctional (meth) acrylic acid esters having 3 or more (meth) acryloyl groups in the molecule (hereinafter also simply referred to as (B32) components)
Monofunctional (meth) acrylate having 1 (meth) acryloyl group (hereinafter also simply referred to as (B33) component)
(B31) Composition of the components
(B31) Specific examples of the component (c) include a component (hereinafter also referred to as a (B31 a) component) represented by the following formula (1), a component (hereinafter also referred to as a (B31B) component) represented by the following formula (2), a component (hereinafter also referred to as a (B31 c) component) represented by the following formula (3), and a 2-functional (meth) acrylate component having a urethane bond (hereinafter also referred to as a (B31 d) component). The component (B31) includes a 2-functional (meth) acrylate component (hereinafter also referred to as a (B31 e) component) which is not a component (B31 a), a component (B31B), a component (B31 c) and a component (B31 d).
Component (B31 a)
(wherein R is 1 R is R 2 Each of a and b is independently an integer of 0 or more, and a+b is an integer of 2 or more. )
If the compound represented by the above formula (1) is specifically exemplified, it is as follows.
Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentapropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, dimethacrylates formed from mixtures of polypropylene glycol and polyethylene glycol (polyethylene having 2 repeating units, polypropylene having 2 repeating units), polyethylene glycol dimethacrylates (especially a=4, b=0, average molecular weight 330), polyethylene glycol dimethacrylates (especially a= 9,b =0, average molecular weight 536), polyethylene glycol dimethacrylates (especially a=14, b=0, average molecular weight 736), tripropylene glycol dimethacrylates, tetrapropylene glycol dimethacrylates, polypropylene glycol dimethacrylates (especially a=0, b=7, average molecular weight 536), polyethylene glycol diacrylates (especially average molecular weight 258), polyethylene glycol diacrylates (especially a=4, b=0, average molecular weight 308), polyethylene glycol diacrylates (especially a= 9,b, average molecular weight 508), polyethylene glycol diacrylates (especially a=0, average molecular weight 708, especially a=9, b=0, average molecular weight 522).
Component (B31B)
(in the formula (I),
R 3 r is R 4 Is a hydrogen atom or a methyl group respectively,
R 5 r is R 6 Is a hydrogen atom or a methyl group respectively,
R 7 is a hydrogen atom or a halogen atom,
a is-O-, -S-, -SO 2 )-、-CO-、-CH 2 -、-CH＝CH-、-C(CH 3 ) 2 -、-C(CH 3 )(C 6 H 5 ) Any one of the above-mentioned,
c and d are integers of 1 or more, and c+d is 2 or more and 30 or less on average. ) The 2-functional (meth) acrylate represented by the above formula (2) is usually obtained as a mixture of molecules having different molecular weights. Thus, c and d are represented as average values.
Specific examples of the 2-functional (meth) acrylate represented by the above formula (2) include the following bisphenol A di (meth) acrylate.
2, 2-bis [4- (methacryloyloxyethoxy) phenyl ] propane (c+d=2, average molecular weight 452), 2-bis [4- (methacryloyloxydiethoxy) phenyl ] propane (c+d=4, average molecular weight 540), 2-bis [4- (methacryloyloxypolyethoxy) phenyl ] propane (c+d=7, average molecular weight 672), 2-bis [3, 5-dibromo-4- (methacryloyloxyethoxy) phenyl ] propane (c+d=2, average molecular weight 768), 2-bis (4- (methacryloyloxydipropyloxy) phenyl) propane (c+d=4, average molecular weight 596), 2-bis [4- (acryloxydiethoxy) phenyl ] propane (c+d=4, average molecular weight 512), 2-bis [4- (acryloxypolyethoxy) phenyl ] propane (c+d=3, average molecular weight 466), 2-bis [4- (acryloxypolyethoxy) phenyl ] propane (c+d=7, average molecular weight 642), 2-bis [4- (methacryloxypolyethoxy) phenyl ] propane (c+d=10, average molecular weight 804), 2-bis [4- (methacryloxypolyethoxy) phenyl ] propane (c+d=17, average molecular weight 1116), 2-bis [4- (methacryloxypolyethoxy) phenyl ] propane (c+d=30, average molecular weight 1684), 2-bis [4- (acryloxypolyethoxy) phenyl ] propane (c+d=10, average molecular weight 776), 2-bis [4- (acryloxypolyethoxy) phenyl ] propane (c+d=20, average molecular weight 1216).
Component (B31 c)
(in the formula (I),
R 8 r is R 9 Is a hydrogen atom or a methyl group respectively,
e is a number of 1 to 20 in terms of average value,
b and B ' may be the same or different and each is a linear or branched alkylene group having 2 to 15 carbon atoms, and when a plurality of B's are present, the plurality of B's may be the same group or different groups. )
The 2-functional (meth) acrylate represented by the above formula (3) can be produced by reacting a polycarbonate diol with (meth) acrylic acid.
The polycarbonate diol used herein may be exemplified by the following. Specifically, there may be mentioned a polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of trimethylene glycol, a polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of tetramethylene glycol, a polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of pentamethylene glycol, a polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of hexamethylene glycol, a polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of octamethylene glycol, a polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of nonamethylene glycol, a polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of triethylene glycol and tetramethylene glycol, a polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of tetramethylene glycol and hexamethyleneglycol, a polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of pentamethylene glycol and octamethylene glycol, a polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of tetramethylene glycol and octamethylene glycol, and a polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of hexamethylene glycol and octamethylene glycol.
Component (B31 d)
The (B31 d) component is typically the reaction product of a polyol and a polyisocyanate. Examples of the polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2, 4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, and methylcyclohexane diisocyanate.
Examples of the polyhydric alcohol include a polyalkylene glycol having a repeating unit of ethylene oxide, propylene oxide or hexane oxide having 2 to 4 carbon atoms, and a polyester glycol such as polycaprolactone glycol. Further, polycarbonate diol, polybutadiene diol or pentaerythritol, ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, 1, 8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, glycerol, trimethylolpropane and the like can be exemplified.
In addition, urethane (meth) acrylates and the like may be used as a reaction mixture in which a urethane prepolymer produced by the reaction of these polyisocyanates and polyols is further reacted with 2-hydroxy (meth) acrylate, or as a reaction mixture in which diisocyanate is directly reacted with 2-hydroxy (meth) acrylate.
As the 2-functional substance, there may be mentioned U-2PPA (molecular weight 482), UA-122P (molecular weight 1100), U-122P (molecular weight 1100) and Daicel-UCB Co., ltd., EB4858 (molecular weight 454) of Nippon Caesalpinia, TEAI-1000 of Japan, TE-2000 and CN9014 of Arkema, which are commercially available.
(B31 e) component
The component (B31 e) may be a compound having (meth) acryloyl groups at both ends of an alkylene group which may have a substituent. Among them, a substance having an alkylene group having 6 to 20 carbon atoms is preferable. Specifically, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol diacrylate, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol diacrylate, 1, 10-decanediol dimethacrylate, and the like are exemplified.
Further, as the component (B31 e), there is also mentioned butadiene di (meth) acrylate represented by the following formula (4).
(in the formula (I),
R 10 r is R 11 Is a hydrogen atom or a methyl group respectively,
f. g and h are each independently integers of 0 or more, and f+g+h is an integer of 1 or more. )
The 2-functional (meth) acrylate represented by the above formula (4) is not particularly limited, and examples of the commercial products include butadiene di (meth) acrylates such as BAC-45 manufactured by Osaka organic chemical industry Co., ltd., CN307 manufactured by Arkema Co.
Further, as the component (B31 e), a 2-functional (meth) acrylate containing a sulfur atom may be mentioned. The sulfur atom preferably forms part of a molecular chain in the form of a thiol group. Specifically, bis (2-methacryloyloxyethyl thioethyl) sulfide, bis (methacryloyloxyethyl) sulfide, bis (acryloyloxyethyl) sulfide, 1, 2-bis (methacryloyloxyethyl thioisopropyl) sulfide, 1, 2-bis (acryloyloxyethyl) sulfide, bis (2-methacryloyloxyethyl thioethyl) sulfide, bis (2-acryloyloxyethyl thioethyl) sulfide, 1, 2-bis (methacryloyloxyethyl thioethyl) thioethane, 1, 2-bis (acryloyloxyethyl thioethyl) sulfide, 1, 2-bis (acryloyloxyisopropyl thioisopropyl) sulfide, and 1, 2-bis (acryloyloxyisopropyl thioisopropyl) sulfide can be exemplified.
The above component (B31 a), component (B31B), component (B31 c), component (B31 d) and component (B31 e) may be either a single component or a plurality of components. When a plurality of substances are used, the mass as a reference of the component (B31) is the total amount of the plurality of substances. The total amount of the component (B31) is not particularly limited, but it is preferably 30 to 100 parts by mass, the component (B31B) is 0 to 70 parts by mass, the component (B31 c) is 0 to 70 parts by mass, the component (B31 d) is 0 to 70 parts by mass, and the component (B31 e) is 0 to 70 parts by mass, and it is more preferably 40 to 95 parts by mass, the component (B31B) is 0 to 50 parts by mass, the component (B31 c) is 5 to 60 parts by mass, the component (B31 d) is 0 to 50 parts by mass, and the component (B31 e) is 0 to 50 parts by mass, based on 100 parts by mass of the component (B31).
(B32) Composition of the components
Examples of the component (B32) include a component (hereinafter also referred to as a (B32 a) component represented by the following formula (5), a polyfunctional (meth) acrylate having a urethane bond (hereinafter also referred to as a (B32B) component), and a polyfunctional (meth) acrylate not belonging to the (B32 a) component and the (B32B) component (hereinafter also referred to as a (B32 c) component).
Component (B32 a)
(in the formula (I),
R 12 is a hydrogen atom or a methyl group,
R 13 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
R 14 is an organic group having 3 to 6 valences and 1 to 10 carbon atoms,
i is a number of 0 to 3 in average value, and j is a number of 3 to 6. )
As R 13 The alkyl group having 1 to 2 carbon atoms is preferably a methyl group. As R 14 Examples of the organic group include a group derived from a polyol, a hydrocarbon group having 3 to 6 valences, and an organic group having 3 to 6 valences and containing a urethane bond.
If the compound represented by the above formula (5) is specifically shown, it is shown below.
Trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, di (trimethylolpropane) propane tetramethacrylate, di (trimethylolpropane) propane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate.
Component (B32B)
The component (B32B) is obtained by reacting the polyisocyanate compound described in the component (B31 d) with a polyol compound, and is a compound having 3 or more (meth) acryloyl groups in the molecule. Examples of the commercial products include U-4HA (molecular weight 596, number of functional groups 4), U-6HA (molecular weight 1019, number of functional groups 6), U-6LPA (molecular weight 818, number of functional groups 6), and U-15HA (molecular weight 2300, number of functional groups 15) manufactured by Xinzhou chemical industries Co.
Component (B32 c)
Examples of the component (B32 c) include a compound obtained by modifying the terminal of a polyester compound with a (meth) acryloyl group. Depending on the molecular weight of the polyester compound as a raw material and the modified amount of the (meth) acryl, various polyester (meth) acrylate compounds can be used as commercially available products. Specifically, there may be mentioned 4-functional polyester oligomers (molecular weight 2500 to 3500, daicel-UCB Co., ltd., EB80, etc.), 6-functional polyester oligomers (molecular weight 6000 to 8000, daicel-UCB Co., ltd., EB450, etc.), 6-functional polyester oligomers (molecular weight 45000 to 55000, daicel-UCB Co., ltd., EB1830, etc.), 4-functional polyester oligomers (in particular GX8488B, etc. of first Industrial pharmaceutical Co., molecular weight 10000), etc. Further, examples of commercial products include CN2300, CN2301, CN2302, CN2303, CN2304, SB401, SB402, SB404, SB500E50, SB500K60, SB510E35, SB520M35, CN550, CN551, A-DPH-6E, A-DPH-12E, A-DPH-6EL, A-DPH-12EL, A-DPH-6P manufactured by Xinzhongcun chemical Co., ltd.
By using the above example (B32) component ((B32 a), component (B32B) and component (B32 c)), the crosslinking density is increased due to polymerization, and the surface hardness of the resulting cured product can be increased. Therefore, in particular, when a photochromic cured product (laminate) obtained by a coating method is formed, the component (B32) is preferably contained.
The above component (B32 a), component (B32B) and component (B32 c) may be either individual components or a plurality of components. When a plurality of substances are used, the mass as a reference of the component (B32) is the total amount of the plurality of substances. Although not particularly limited, when the total amount of the component (B32) is 100 parts by mass, it is preferable that the component (B32 a) is 50 to 100 parts by mass, the component (B32B) is 0 to 50 parts by mass, and the component (B32 c) is 0 to 50 parts by mass.
(B33) Composition of the components
The component (B33) may be a compound represented by the following formula (7).
(in the formula (I),
R 16 is a hydrogen atom or a methyl group,
R 17 is a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group or a glycidyl group,
l is an integer of 0 to 10, and m is an integer of 0 to 20. )
If the compound represented by the above formula (7) is specifically shown, it is shown below.
Methoxy polyethylene glycol methacrylate (particularly average molecular weight 293), methoxy polyethylene glycol methacrylate (particularly average molecular weight 468), methoxy polyethylene glycol acrylate (particularly average molecular weight 218), methoxy polyethylene glycol acrylate (particularly average molecular weight 454), stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, gamma-methacryloxypropyl trimethoxysilane, gamma-methacryloxypropyl methyldimethoxysilane, glycidyl methacrylate, tridecyl acrylate, tridecyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, isodecyl methacrylate.
(B) Preferred compounding ratio of the ingredients
(B) The component (B) preferably contains a component (B1), a component (B2), and a component (B3).
When the component (B) contains only the component (B3), the total amount of the component (B) is preferably 30 to 80 parts by mass, the component (B32) is preferably 10 to 60 parts by mass, and the component (B33) is preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the total amount of the component (B). The component (B31) is preferably 40 to 75 parts by mass, the component (B32) is preferably 15 to 55 parts by mass, and the component (B33) is preferably 0.5 to 10 parts by mass.
When the component (B1) is contained and the component (B2) is not contained, the amount of the component (B1) is preferably 0.1 to 20 parts by mass, the component (B31) is preferably 30 to 80 parts by mass, the component (B32) is preferably 10 to 60 parts by mass, and the component (B33) is preferably 0.1 to 10 parts by mass, based on 100 parts by mass. The component (B1) is preferably 0.5 to 10 parts by mass, the component (B31) is preferably 40 to 75 parts by mass, the component (B32) is preferably 15 to 55 parts by mass, and the component (B33) is preferably 0.5 to 10 parts by mass.
When the component (B2) is contained and the component (B1) is not contained, the amount of the component (B2) is preferably 0.1 to 8 parts by mass, the component (B31) is preferably 30 to 80 parts by mass, the component (B32) is preferably 10 to 60 parts by mass, and the component (B33) is preferably 0.1 to 20 parts by mass, based on 100 parts by mass. The component (B2) is preferably 0.1 to 6 parts by mass, the component (B31) is preferably 40 to 75 parts by mass, the component (B32) is preferably 15 to 55 parts by mass, and the component (B33) is preferably 0.5 to 10 parts by mass.
When both the component (B1) and the component (B2) are contained, the amount of the component (B1) is preferably 0.1 to 20 parts by mass, the component (B2) is preferably 0.1 to 8 parts by mass, the component (B31) is 30 to 80 parts by mass, the component (B32) is preferably 10 to 60 parts by mass, and the component (B33) is preferably 0.1 to 20 parts by mass, based on 100 parts by mass. Further preferably, the component (B1) is 0.5 to 10 parts by mass, the component (B2) is 0.1 to 6 parts by mass, the component (B31) is 40 to 75 parts by mass, the component (B32) is 15 to 55 parts by mass, and the component (B33) is 0.5 to 10 parts by mass.
In view of compatibility with other components, solubility, and coatability of the photochromic curable composition, and coatability of the polyurethane resin layer laminated on the optical substrate, the SP value of the component (B) is preferably 7.0 to 12.0. (B) The SP value of the component can be determined by titration based on the turbidity titration method described in detail below. The SP value can be calculated from the solubility parameter δ recorded in the chemical review application written by the japan chemical society (journal 1973) and Polymer Handbook (4 th edition, johannnes Brandrup and e.h. immergut, 1998).
Although it is presumed that the SP value of the component (B) is close to the SP value of the component (A), excellent effects can be exhibited. In order to exert more excellent effects, the SP value of the component (B) is more preferably 7.5 to 12.0, still more preferably 7.5 to 11.5, particularly preferably 8.0 to 11.0.
Component (C)
As the component (C), known ones may be used without any limitation, and 1 kind of them may be used alone or 2 or more kinds of them may be used in combination.
Representative examples of the photochromic compounds include fulgide compounds, chromene compounds and spirooxazine compounds, and are disclosed in various documents such as Japanese patent application laid-open No. 2-28154, japanese patent application laid-open No. 62-288830, WO94/22850 and WO 96/14596.
Among known photochromic compounds, those having an indeno [ 2,1-f ] naphtho [ 1,2-b ] pyran skeleton are more preferably used from the standpoint of photochromic properties such as color development concentration, initial colorability, durability, fading speed, etc., and particularly those having a molecular weight of 540 or more are particularly excellent in color development concentration and fading speed, and therefore are preferably used.
The chromene compounds shown below are examples of chromene compounds particularly preferably used in the present invention, but are not limited thereto.
In addition to the above, a photochromic compound having an oligomer chain group in the molecule can be preferably used. As such a photochromic compound having an oligomer chain group, there are disclosed various documents such as WO2000/015630 pamphlet, WO 2004/04961 pamphlet, WO2009/146509 pamphlet, WO2012/149599 pamphlet, WO2012/162725 pamphlet, WO2013/078086 pamphlet, WO 2019/013049 pamphlet, and WO2019/203205 pamphlet. Among these photochromic compounds having an oligomer chain group in the molecule, those having an oligomer chain group described in WO 2019/01349 or WO2019/203205 are preferably used for the purpose of exhibiting more excellent photochromic properties and durability. Examples of particularly preferred photochromic compounds include, but are not limited to, those having an oligomer chain group.
The component (C) may be a compound having a group having a long chain having a molecular weight of 300 or more as a substituent. The molecular weight of 300 or more means the molecular weight of only a long chain portion. The long chain is preferably at least one group selected from the group consisting of polysiloxane chain, polyoxyalkylene chain, polyester chain and polyester polyether chain. The long chain having a molecular weight of 300 or more may be constituted by 1 kind of repeating structure, or may be a block copolymer or a graft copolymer having a plurality of kinds of repeating structures. When the long chain is a copolymer having a plurality of repeating structures, the molecular weight of the long chain means the average molecular weight of each repeating structure. The average value is a number average molecular weight. The molecular weight can be confirmed by the kind of raw material used in the production of the photochromic compound. In addition, when the product is confirmed by the production, the product can be confirmed by known means such as NMR, IR, mass analysis, and the like.
It is considered that the component (C) has a long chain group having a molecular weight of 300 or more, and that the component (B) can exhibit higher photochromic characteristics. The molecular weight of the long chain group is preferably 300 to 25000, more preferably 400 to 20000, further preferably 440 to 15000, particularly preferably 500 to 10000, in view of photochromic properties, the compounding amount thereof and the productivity of the component (C) itself.
The number of the long chain groups is preferably at least 0.5 or more relative to the molecule of the photochromic compound 1. That is, a photochromic compound having a structure in which 2 photochromic sites are bonded via a group containing a long chain can be used. In view of balance with molecular weight of the molecular chain, photochromic property, and the like, the number of long-chain groups per 1 molecule of the photochromic site is preferably 4 or less, more preferably 2 or less, and further preferably 1.
In view of photochromic properties such as the color development concentration and the fading speed of the obtained photochromic cured product, the blending amount of the component (C) is preferably the following blending amount. That is, the amount of component (C) to be blended is preferably 0.001 parts by mass or more and 20 parts by mass or less, more preferably 0.05 parts by mass or more and 15 parts by mass or less, and still more preferably 0.1 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of component (B).
Component (D)
The photochromic curable composition of the embodiment may further comprise an organic compound having a boiling point of 80 ℃ to 200 ℃ and an SP value of 8.0 to 10.0. Hereinafter, this organic compound is also referred to as component (D). The SP value referred to herein is a value sometimes referred to as a solubility parameter, a hildebrand parameter, or the like.
When the curable composition containing the component (D) is used, the appearance of the cured product can be improved. That is, component (D) has a relatively high boiling point, and therefore can be left in a trace amount in the cured product. (D) The SP value of the component is in the above range, and therefore, compatibility with the acrylic adhesive of the protective film is high. Therefore, when the acrylic adhesive flowing out from the adhesive surface of the protective film is impregnated into the photochromic resin layer, a small amount of the component (D) remaining in the photochromic resin layer is compatible with the acrylic adhesive as a foreign substance. This prevents the acrylic adhesive from accumulating inside the photochromic resin layer. Therefore, the appearance defects of the fine lines and stripes which are visible inside the photochromic resin layer due to the acrylic adhesive are less likely to occur.
(D) The SP value of the component is preferably 8.0 to 9.5, more preferably 8.0 to 9.0. (D) When the SP value of the component is within this range, the coating easiness of the curable composition tends to be improved, and the productivity tends to be improved.
(D) The boiling point of the component (A) is preferably 85 ℃ to 200 ℃, more preferably 95 ℃ to 200 ℃, still more preferably 110 ℃ to 170 ℃. (D) When the boiling point of the component is high, the appearance of the cured product tends to be improved. When the boiling point of the component (D) is low, the adhesion and durability of the cured product tend to be improved.
The component (D) is not particularly limited as long as the SP value and the boiling point satisfy the ranges, but the following organic compounds are preferable in view of the compatibility with the preferable component (B) described below. Specifically, preferable organic compounds include:
aromatic compounds such as toluene (boiling point 111 ℃, SP value 8.8), xylene (boiling point 138 ℃, SP value 8.7), and styrene (boiling point 145 ℃, SP value 8.5);
ketone compounds such as methyl propyl ketone (boiling point 105 ℃, SP value 8.7), methyl isopropyl ketone (boiling point 95 ℃, SP value 8.5), diethyl ketone (boiling point 101 ℃, SP value 8.8), methyl isobutyl ketone (boiling point 116 ℃, SP value 8.4);
ester compounds such as butyl acetate (boiling point 124 ℃, SP value 8.5), isopropyl acetate (boiling point 89 ℃, SP value 8.4), isobutyl acetate (boiling point 116 ℃, SP value 8.3), ethyl acetate (boiling point 80 ℃, SP value 9.1);
ether compounds such as diethylene glycol dimethyl ether (boiling point 162 ℃, SP value 9.9) and propylene glycol monomethyl ether (boiling point 120 ℃, SP value 9.1);
cyclic alkyl compounds such as cyclohexane (boiling point 81 ℃, SP value 8.2); etc. Commercially available products can also be used for these substances.
Among them, from the viewpoint of compatibility with the component (B), the component (D) preferably contains at least 1 selected from the group consisting of an ether compound, an ester compound, an aromatic compound, a ketone compound and a cyclic alkyl compound, and further preferably contains at least 1 selected from the group consisting of an ester compound and an aromatic compound. Among them, butyl acetate, toluene or xylene is preferable, toluene or xylene is more preferable, and xylene is particularly preferable. Xylene may also be a mixture comprising isomers.
These (D) components may be used alone or in combination of 1 or more than 2. When 2 or more types of the components (D) are used, the reference amount of the components (D) is the total amount of the components (D). The styrene and methyl methacrylate listed here have radical polymerizable groups, but are contained in the component (D).
The amount of the component (D) is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the component (B). When the amount of the component (D) is within this range, compatibility with the component (B) can be improved, and smoothness of the resulting photochromic layer can be further improved. As a result, occurrence of appearance defects can be further suppressed. In addition, the adhesion and durability of the photochromic resin layer can be improved. The component (D) is more preferably 0.5 to 9 parts by mass, particularly preferably 1.0 to 6 parts by mass, based on 100 parts by mass of the component (B).
Component (E)
The curable composition of the embodiment may further contain a hindered amine component as the (E) component. Hindered amines function as light stabilizers. When the curable composition containing the component (E) is used, the durability of the cured product is improved. The following components (E1) and (E2) are examples of the component (E). One of the component (E1) and the component (E2) may be contained, but both are preferably contained.
(E1) Composition of the components
(E1) The component (a) is a reactive hindered amine compound having at least 1 reactive group selected from the group consisting of a radically polymerizable group and a group reactive with the radically polymerizable group. When such a component (E1) is used, the appearance of the cured product tends to be further improved. The reason for this will be described below. First, hindered amine-based light stabilizers (HALS: hindered Amine Light Stabilizers) sometimes permeate from the cured product to the surface thereof over time, so-called bleed-out. Further, it is considered that HALS has high affinity with the acrylic adhesive used for the protective film. Therefore, when a curable composition containing HALS is used, the light stability is improved, and the acrylic adhesive is likely to penetrate into the photochromic resin layer. For such problems, the (E1) component has a radical reactive group. Therefore, it is considered that the component (E1) is in a state of forming a complex with the component (B) in the cured product, similarly to the component (a), and thus bleeding out to the surface of the photochromic resin layer can be reduced. Therefore, when the component (E1) is contained, the acrylic adhesive derived from the protective film is more difficult to penetrate into the photochromic resin layer, and the appearance of the cured product is less likely to be poor.
(E1) Examples of the radical polymerizable group in the component (a) include a (meth) acryl group (a methacryl group and/or an acryl group), a vinyl group, and the like. Examples of the group reactive with the radical polymerizable group include a thiol group, an amino group, and an epoxy group.
(E1) The component preferably has a 1,2, 6-pentamethyl-4-piperidinyl structure. Specifically, a compound represented by the following formula (X) (hereinafter, also referred to as a (E1X) component) is preferable.
In the formula (X), the amino acid sequence of the formula (X),
R 100 r is R 300 Is a hydrogen atom or a methyl group respectively,
x is a group represented by the following formula (Z),
R 200 is an alkylene group having 1 to 5 carbon atoms,
t is a number of 0 to 20 in terms of average value,
u is a number of 0 to 20 in terms of average value,
in the formula (Z) of the present invention,
R 400 is an alkylene group having 1 to 20 carbon atoms,
v is a number of 0 to 20 in average value.
In the above formula, t, u, and v are represented by average values, and are often obtained in the form of a mixture in production.
In the formula (X), R 300 Preferably methyl. R is R 100 Is a hydrogen atom or a methyl group.
X is a 2-valent group represented by the formula (Z). In the formula (Z), R 400 The alkylene group may be a straight chain or branched alkylene group having 1 to 20 carbon atoms. Wherein R is 400 The straight-chain or branched alkylene group having 1 to 10 carbon atoms is preferable, and the straight-chain or branched alkylene group having 1 to 3 carbon atoms is more preferable. In order to exert excellent effects, v is preferably small, preferably a number of 0 to 10 on average, and more preferably a number of 0 to 5 on average.
R 200 The alkylene group may be a straight chain or branched alkylene group having 1 to 10 carbon atoms. In order to exert excellent effects, a linear or branched alkylene group having 1 to 5 carbon atoms is more preferable. In order to exert excellent effects, t is preferably small, preferably a number of 0 to 10 on average, and more preferably a number of 0 to 5 on average.
u is a number of 0 to 20 in terms of average value. Among them, u is preferably small, preferably a number of 0 to 3 on average, and preferably a number of 0 to 2 on average, in order to exert an excellent effect.
The component (E1X) is a known compound, and commercially available products can be used. Specifically, LA-82 and LA-87 manufactured by ADEKA Co., ltd.
Among the components (E1X), R is particularly preferable as a substance capable of exerting particularly excellent effects 100 R is R 300 A compound which is methyl and t, u, v are 0 (X is an oxygen atom).
Specifically, 1,2, 6, -pentamethyl-4-piperidinyl methacrylate is preferable. In the component (E1X), the 1,2, 6-pentamethyl-4-piperidyl methacrylate can highly maintain the stability of the photochromic curable composition itself and the stability of the photochromic optical article even if the compounding amount is small.
When the curable composition according to the embodiment contains the component (E1), the amount of the component (E1) is preferably 0.5 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 3.0 parts by mass or less, based on 100 parts by mass of the component (B).
(E2) Composition of the components
(E2) The component (c) is a non-reactive hindered amine compound having no reactive group selected from the group consisting of a free radically polymerizable group and a group reactive with the free radically polymerizable group. That is, the component (E2) is a conventionally commonly used HALS. In the photochromic resin layer which is a cured product of the curable composition, the light stability effect of the (E2) component is considered to be higher than that of the (E1) component. From the viewpoint of further improving the appearance of the cured product, it is preferable to blend the component (E1) in the curable composition in addition to the component (E2).
(E2) The component (c) is not particularly limited, but a compound represented by the following formula (Y) (hereinafter, may be abbreviated as "(E2Y component").
In the formula (Y), the amino acid sequence of the formula (Y),
R 500 r is R 600 Is a hydrogen atom or a methyl group respectively,
w is an integer of 1 to 50.
Of the components (E2Y), R is preferable 500 R is R 600 Is methyl, bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate with w being 8. When the (E2Y) component is used, a substance containing bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate as the (E2Y) component and (1, 2, 6-pentamethyl-4-piperidinyl) sebacate inevitably contained therein may be used as the (E2) component. In this case, the component (E2) is compounded in the amount of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate and (1, 2, 6-pentamethyl-4-piperidinyl) sebacate The total amount of esters is taken as a reference. Of course, (1, 2, 6-pentamethyl-4-piperidinyl) sebacate belongs to the (E2) component other than the (E2Y) component.
(E2) The component (c) may be composed of only the (E2Y) component or may be composed of the (E2Y) component and (1, 2, 6-pentamethyl-4-piperidinyl) sebacate. The composition may contain a component (E2Y) and a component (E2) other than the component (E2Y) (1, 2, 6-pentamethyl-4-piperidinyl) sebacate. The (E2) component may contain a component (E2) other than the (E2Y) component and the (1, 2, 6-pentamethyl-4-piperidinyl) sebacate. In order to exert more excellent effects, the (E2) component is a solution containing bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate as the (E2Y) component and may also contain (1, 2, 6-pentamethyl-4-piperidinyl) sebacate.
When the curable composition according to the embodiment contains the component (E2), the amount of the component (E2) is preferably 0.1 part by mass or more and 5.0 parts by mass or less, and more preferably 0.1 part by mass or more and 3.0 parts by mass or less, based on 100 parts by mass of the component (B).
(E) Preferred blending ratio of the (E1) component and the (E2) component in the component
When the component (E1) is 100 parts by mass, the component (E) preferably contains 0 to 500 parts by mass of the component (E2). By satisfying this range, the appearance defect derived from the protective film for scratch prevention can be sufficiently suppressed, and the durability of repetition is good. Further, in view of photochromic properties, storage stability, other properties, and the like, it is preferable to include both the (E1) component and the (E2) component. When the curable composition of the embodiment contains both the (E1) and (E2) components, the (E2) component is preferably contained in an amount of 1 to 300 parts by mass, more preferably 1 to 200 parts by mass, still more preferably 1 to 150 parts by mass, and particularly preferably 1 to 100 parts by mass, based on 100 parts by mass of the (E1) component.
(E) Preferred compounding ratio of the ingredients
The amount of the component (E) is preferably 0.1 parts by mass or more and 5.0 parts by mass or less relative to 100 parts by mass of the component (B). By satisfying this range, good photochromic characteristics and repetition durability can be obtained, and storage stability is good. Further, in order to improve the storage stability, it is more preferably 0.5 parts by mass or more and 4.0 parts by mass or less, still more preferably 1.0 parts by mass or more and 3.5 parts by mass or less, and particularly preferably 1.0 parts by mass or more and 2.8 parts by mass or less.
< additive >)
The photochromic curable composition of the embodiment may contain various additives known per se within a range not impairing the effect. Examples of the additive include a polymerization initiator, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, an anti-coloring agent, an antistatic agent, a fluorescent dye, a pigment, a perfume, a stabilizer, a solvent, and a leveling agent.
The amount of the additive is, for example, in the range of 0.001 to 10 parts by mass, particularly 0.01 to 7.5 parts by mass, and further 0.05 to 6 parts by mass, based on 100 parts by mass of the component (B).
Polymerization initiator
The polymerization initiator includes a thermal polymerization initiator and a photopolymerization initiator, and specific examples thereof are as follows.
The thermal polymerization initiator may be exemplified by
Diacyl peroxides: benzoyl peroxide, benzoyl p-chloroperoxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide;
peroxyesters: tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, tert-butyl peroxybenzoate;
percarbonate: diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate;
azo compound: azobisisobutyronitrile; etc.
The photopolymerization initiator may be exemplified by
Acetophenone-based compounds: 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one;
alpha-dicarbonyl compound: 1, 2-diphenylethanedione and methyl phenylglyoxylate;
acyl phosphine oxide-based compound: 2, 6-dimethylbenzoyl diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, methyl 2,4, 6-trimethylbenzoyl diphenyl phosphonate, 2, 6-dichlorobenzoyl diphenyl phosphine oxide, 2, 6-dimethoxybenzoyl diphenyl phosphine oxide.
When a photopolymerization initiator is used, a known polymerization curing accelerator such as a tertiary amine may be used in combination.
Ultraviolet stabilizer
The ultraviolet stabilizer is preferably used because it can improve the durability of the photochromic compound. The ultraviolet stabilizer herein does not include the component (A). As such ultraviolet stabilizers, hindered phenol antioxidants, sulfur antioxidants, and the like are known. Particularly preferred ultraviolet stabilizers are as follows. 2, 6-di-tert-butyl-4-methyl-phenol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ], ciba Specialty Chemicals, IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, 254, 245, manufactured by inc.
The amount of the ultraviolet stabilizer used is not particularly limited as long as the effect of the present invention is not impaired, and is in the range of 0.001 to 10 parts by mass, particularly 0.01 to 3 parts by mass, relative to 100 parts by mass of the component (B).
Leveling agent
In addition, the photochromic curable composition of the embodiment may be blended with a leveling agent such as a non-reactive silicone oil within a range that does not inhibit the effect. The non-reactive silicone oil is not particularly limited, and commercially available KF-351A, KF-352A, FL-5, X-22-821, X-22-822, KF-412, KF-414, dow Corning Toray Co.Ltd. Manufactured by Xinyue chemical industry Co., ltd., L7001, FZ2104, FZ2110 and the like can be used. In addition, reactive leveling agents having no siloxane bond may be compounded. The reactive leveling agent is not particularly limited, and commercially available ADEKA REASUPASASP SR-10, SR-20, SR-1025, SR-3025, ER-10, ER-20, ER-30, ER-40, NE-10, NE-20, etc. manufactured by ADEKA Co., ltd can be used. As described above, when these leveling agents are used, the appearance of the photochromic cured product may be degraded. In the photochromic curable composition of the embodiment, since the component (a) functions as a leveling agent, the amount of these conventional leveling agents can be reduced or a photochromic resin layer excellent in smoothness can be obtained even if not used. When the curable composition according to the embodiment contains the non-reactive silicone oil, the amount thereof is preferably 1 part by mass or less, more preferably 0.5 part by mass or less, per 100 parts by mass of the component (B). The curable composition according to a further preferred embodiment does not contain a non-reactive silicone oil, and is 0 parts by mass per 100 parts by mass of the component (B).
Catalyst
In the photochromic curable composition of the embodiment, a catalyst may be blended so as to react the radical polymerizable group with a group reactive with the radical polymerizable group within a range that does not inhibit the effect. The catalyst is not particularly limited, and for example, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tri-n-propylphosphine, hexylamine, dipropylamine, triethylamine, 1, 8-bis (dimethylamino) naphthalene, diazabicycloundecene, diazabicyclononene and the like can be used. When these catalysts are used, the durability of the photochromic cured product may be reduced. The amount of the catalyst in the curable composition according to the embodiment is not particularly limited, but is preferably 0.000001 parts by mass or more and 5 parts by mass or less, more preferably 0.00001 parts by mass or more and 3 parts by mass or less, and particularly preferably 0.00001 parts by mass or more and 2 parts by mass or less, based on 100 parts by mass of the component (a).
Process for producing photochromic curable composition
The photochromic curable composition of the embodiment can be produced by mixing the component (a), the component (B), the component (C), and other additive components (including the component (D) and the component (E)) which are optionally blended. The mixing order of the components is not particularly limited. Wherein the component (B) and the component (C) are mixed, and the component (E) is added as needed in a state where the component (C) is sufficiently dispersed in the component (B). The component (A) and the component (D) may be further mixed as needed. At this time, other additive components may be compounded at any point in time.
In addition, the SP value of the photochromic curable composition is not particularly limited. In view of the ability to uniformly disperse the components, the coatability of the photochromic curable composition, and the coatability of the polyurethane resin layer laminated on the optical substrate, it is preferably 7.0 to 12.0, more preferably 7.5 to 12.0, still more preferably 7.5 to 11.5, and particularly preferably 8.0 to 11.0. The SP value can be determined by titration based on the turbidity titration method described in detail below.
< photochromic cured article >)
The photochromic cured product can be obtained by curing a photochromic curable composition.
The photochromic curable composition may be cured by causing radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays, α rays, β rays, γ rays, LEDs, or the like, heat, or a combination of both. That is, an appropriate curing means may be employed depending on the type of polymerizable monomer and polymerization curing accelerator used and the form of the photochromic cured product to be formed. When the photochromic laminate is formed by a coating method described later, photopolymerization is preferably used for the reason that a uniform film thickness can be obtained.
When the photochromic curable composition is photopolymerized, the properties of the resulting photochromic laminate are affected by, in particular, UV intensity under curing conditions. The illuminance condition is affected by the type and amount of the photopolymerization initiator and the type of polymerizable monomer, and therefore cannot be generalized, but it is generally preferable to irradiate the light at 365nm for 0.1 to 5 minutes with 10 to 500mW/cm 2 The conditions are chosen in such a way that UV light is emitted. The curable composition of the embodiment contains the component (a), and therefore can suppress the alignment of the leveling agent on the surface of the cured product. Therefore, the curable composition can be sufficiently cured without excessively enhancing the intensity of UV light, and the alignment of the leveling agent can be suppressed, thereby improving the production efficiency.
< photochromic laminate >)
The photochromic laminate includes an optical base material, a photochromic resin layer which is a cured product of the curable composition, and a polyurethane resin layer which is located between the optical base material and the photochromic resin layer. The polyurethane resin layer may be omitted.
When a photochromic laminate is obtained by a coating method, a photochromic curable composition is used as a coating liquid, the coating liquid is applied to the surface of an optical substrate such as a lens substrate by spin coating, dipping, or the like, and then polymerization curing is performed by UV irradiation, heating, or the like in an inert gas such as nitrogen gas, whereby a laminate in which a photochromic layer formed from a photochromic cured product is laminated on the surface of the optical substrate can be obtained.
Examples of the optical substrate include an optical substrate used for a spectacle lens, a window glass of a house or an automobile, and the like. Specific materials of the optical substrate include plastic materials such as (meth) acrylic resins, polycarbonate resins, allyl resins, thiocarbamate resins, urethane resins, and thiocarboxylic resins, and glasses.
When the photochromic laminate is formed on the surface of the optical substrate by the coating method described above, it is preferable to improve the adhesion between the photochromic laminate and the optical substrate by performing chemical treatment with an alkali solution, an acid solution or the like, physical treatment with corona discharge, plasma discharge, polishing or the like on the surface of the optical substrate in advance. A transparent adhesive resin layer may be provided on the surface of the optical substrate in advance. The transparent adhesive resin layer is preferably a polyurethane resin layer. That is, it is preferable to form a photochromic laminate including a laminate structure in which a urethane resin layer and a resin layer containing a photochromic compound are laminated in this order on the surface of an optical substrate.
The urethane resin layer is preferably formed by applying a coating liquid containing at least 1 component selected from the group consisting of urethane resins and precursors of moisture-curable urethane resins curable by moisture in air, and a solvent having a boiling point of 70 ℃ or higher and an SP value of 8.0 or higher, to the surface of the optical substrate, and then removing the solvent.
Specifically, the photochromic laminate is preferably produced by the following steps. First, the following steps are performed: after coating the surface of the optical substrate with the coating liquid, removing the solvent, thereby forming a polyurethane resin layer; the coating liquid contains at least 1 component selected from the group consisting of polyurethane resins and precursors of moisture-curable urethane resins that can be cured by moisture in the air, and a solvent having a boiling point of 70 ℃ or higher and an SP value of 8.0 or higher.
Commercially available products can be used as the coating liquid. Particularly, a coating liquid containing at least 1 component selected from the group consisting of a polyurethane resin and a precursor of a moisture-curable urethane resin curable by moisture in air, in which the solid content is 15 to 40% by mass, and the solvent having an SP value of 8.0 or more is 60 to 85% by mass, is preferably used (when the total amount of the solid content and the solvent is 100% by mass, any other known component may be blended into the coating liquid).
The solvent having an SP value of 8.0 or more may be the same as the organic compound having an SP value of 8.0 or more in the component (D). Specifically, examples of the solvent having a boiling point of 70 ℃ or higher and an SP value of 8.0 or higher include toluene (boiling point 111 ℃ C., SP value 8.8), xylene (boiling point 138 ℃ C., SP value 8.7), ethyl acetate (boiling point 77 ℃ C., SP value 9.0), methyl propyl ketone (boiling point 105 ℃ C., SP value 8.7), butyl acetate (boiling point 124 ℃ C., SP value 8.5), methyl isopropyl ketone (boiling point 95 ℃ C., SP value 8.5), isopropyl acetate (boiling point 89 ℃ C., SP value 8.4), isobutyl acetate (boiling point 116 ℃ C., SP value 8.3), methyl isobutyl ketone (boiling point 116 ℃ C., SP value 8.5), ethylene glycol dimethyl ether (boiling point 85 ℃ C., SP value 8.6), propylene glycol monoethyl ether acetate (boiling point 146 ℃ C., SP value 8.6), methyl acetoacetate (boiling point 170 ℃ C., SP value 8.4), diethyl ketone (boiling point 101 ℃ C., SP value 8.8), and the like. The solvent may be used in an amount of 1 or 2 or more. When the mixed solvent is used, the total amount of the mixed solvent is based on the total amount of the mixed solvent. The SP value was also the value of the mixed material.
The polyurethane resin layer may be formed by coating a coating liquid on an optical substrate and then removing a solvent. When the precursor of the moisture-curable urethane resin is contained, the urethane resin layer can be formed by curing the precursor with moisture in the air.
The thickness of the urethane resin layer is not particularly limited, but is preferably 2.0 to 10.0 μm.
Then, after the photochromic curable composition is applied to the polyurethane resin layer, the coating film is cured to form a photochromic resin layer. Thus, a photochromic laminate in which the optical substrate and the photochromic resin layer are bonded via the urethane resin layer can be produced. The thickness of the photochromic resin layer is not particularly limited, but is 30 to 50 μm.
In addition, when the photochromic curable composition is applied to the urethane resin layer, a small amount of solvent having a boiling point of 70 ℃ or higher and an SP value of 8.0 or higher may remain on the urethane resin layer. Since the compatibility of the solvent remaining in a trace amount with the component (D) contained in the curable composition is high, when the component (D) is compounded, a photochromic resin layer having more excellent smoothness tends to be obtained and the production efficiency tends to be improved.
The coating method is described, but the photochromic curable composition of the embodiment may be used to produce a photochromic cured product by a known method such as injection polymerization, adhesion, dip coating, flow coating, spraying, or adhesive method.
The photochromic cured product and the laminate according to the embodiment may contain a dye such as a disperse dye according to the application. In addition, a hard coat layer may be further laminated on the photochromic resin layer of the laminate. The hard coat layer can be obtained, for example, by applying a hard coat agent containing an oxide sol of silicon, zirconium, antimony, aluminum, tin, tungsten or the like as a main component and a silane coupling agent onto the photochromic resin layer, and curing the film. Alternatively, siO may be deposited on the photochromic resin layer 2 、TiO 2 、ZrO 2 And metal oxides to form a hard coat layer. Further, a post-treatment such as an anti-reflection treatment or an antistatic treatment may be performed on the photochromic resin layer of the laminate. These post-treatments can be carried out, for example, by applying a coating liquid containing an organic polymer to the photochromic resin layer or the hard coat layer and drying the same to form a thin film.
The vickers hardness of the photochromic cured product (in a state where a hard coat film or the like is not formed) is preferably 3.0 or more and 8.0 or less, more preferably 3.5 or more and 7.5 or less, and particularly preferably 4.0 or more and 7.5 or less.
The surface of the photochromic resin layer of the photochromic laminate may be adhered with a protective film for the purpose of protecting the surface and preventing dust adhesion. In the photochromic cured product of the embodiment, as described above, the component (a) is contained, and thus, appearance defects caused by the acrylic adhesive contained in the protective film are less likely to occur. In order to prevent appearance defects, the SP value of the photochromic curable composition is preferably slightly different from the SP value of the adhesive. The upper limit of the difference in SP value is not particularly limited, but is preferably 5 or less from the viewpoint of adhesion. The difference in SP value is preferably 0.05 to 5.0, more preferably 0.075 to 4.0, particularly preferably 0.1 to 3.0. The SP value of the photochromic curable composition and the SP value of the binder can be obtained by titration based on the turbidity titration method described in examples, as described in detail below.
In order to prevent appearance defects from occurring, it is preferable that the contact angle of the photochromic cured product with respect to the solvent contained in the adhesive surface of the protective film is high. Examples of the solvent contained in the adhesive surface of the protective film include ethylene glycol. Specifically, the contact angle with respect to the solvent is preferably 50 degrees or more. By setting the angle to 50 degrees or more, the above-described appearance defects can be reduced. The upper limit of the contact angle of the photochromic cured product with respect to the solvent is not particularly limited, but is preferably less than 90 degrees. The contact angle is more preferably 50 degrees or more and 0 degrees or less and 90 degrees or less, and still more preferably 50 degrees or more and 85 degrees or less.
Examples
The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the examples. The description and evaluation methods of the respective components are as follows.
< ingredients >
(A) Composition of the components
A1: (trade name: TEGORAD2100, manufactured by Evonik Japan Co., ltd.)
A2: (trade name: TEGORAD2300, manufactured by Evonik Japan Co., ltd.)
A3: (trade name: BYK-UV3500, manufactured by BYK Japan KK)
A4: (trade name: BYK-UV3505, manufactured by BYK Japan KK)
A5: (trade name: BYK-UV3510, manufactured by BYK Japan KK)
A6: (trade name: BYK-UV3530, BYK Japan KK)
A7: (trade name: BYK-UV3535, BYK Japan KK)
A8: (trade name: BYK-UV3570, manufactured by BYK Japan KK)
A9: (trade name: BYK-UV3575, manufactured by BYK Japan KK)
A10: (trade name: BYK-UV3576, manufactured by BYK Japan KK)
A11: (trade name: BYK-3550,BYK Japan KK)
A12: (trade name: BYK-3560,BYK Japan KK)
A13: (trade name: BYK-3565,BYK Japan KK)
A14: (trade name: BYK-3566,BYK Japan KK)
A15: (trade name: KR-511, xinyue chemical industry Co., ltd.)
A16: (trade name: KR-513, manufactured by Xinyue chemical industry Co., ltd.)
A17: ( Trade name: x-40-9296, manufactured by Xinyue chemical industry Co., ltd )
A18: ( Trade name: KF-8012, manufactured by Xinyue chemical industry Co., ltd )
A19: (trade name: DOWSIL BY16-205, manufactured BY Dow Toray Co., ltd.)
A20: (trade name: KR-518, made by Xinyue chemical industry Co., ltd.)
A21: (trade name: KR-516, made by Xinyue chemical industry Co., ltd.)
A22: (trade name: DOWSIL BY16-876, manufactured BY Dow Toray Co., ltd.)
(B) Composition of the components
(B1) Composition of the components
RX-1: polyrotaxane having an acryl group and having the following characteristics
Weight average molecular weight Mw (GPC); 180000.
ratio of acryl modification in side chain: 80 mol%.
The proportion of residual OH groups in the side chains; 20 mol%.
An axial molecule; linear polyethylene glycol (PEG) with molecular weight 11000.
A wrapping ring; the alpha-cyclodextrin (alpha-CD) incorporation ratio was 0.25.
The end of the axin; and (5) end capping of adamantane.
Wrapping the side chain introduced in the ring; the (average) molecular weight of the side chains is about 500.
Number of acryl groups per 1 molecule: about 90.
RX-1 was synthesized by the method described in International publication No. WO 2018/030275. The weight average molecular weight Mw of RX-1 is determined by Gel Permeation Chromatography (GPC). As the apparatus, a liquid chromatography apparatus (manufactured by Waters corporation, japan) was used. As a column, 2 TSKgel SuperHM-M (exclusion limit molecular weight: 4000000, manufactured by Tosoh Co., ltd.) were used in series. Further, the measurement was performed using tetrahydrofuran as a developing solution at a flow rate of 0.6 ml/min and a temperature of 40 ℃. The weight average molecular weight of the standard sample was determined by comparison and conversion using polystyrene.
(B2) Composition of the components
SO-1: silsesquioxane having the following characteristics and having a methacryloyl group.
Number of methacrylate groups per 1 molecule: 20.
Weight average molecular weight; 4800.
acid value; 1.1mgKOH/g.
SO-2: "trade name: AC-SQ SI-20, manufactured by Toyama Synthesis Co., ltd "
Number of acryl groups per 1 molecule: about 4.
Weight average molecular weight; 2000.
the SO-1 was synthesized by the following method. First, 248ml of ethanol and 5 of water were added to 248g (1.0 mol) of 3-trimethoxysilylpropyl methacrylate4g (3.0 mol) of sodium hydroxide (0.20 g, 0.005 mol) was added as a catalyst, and the mixture was reacted at 30℃for 3 hours. By passing through 1 After confirming the disappearance of the starting material by H-NMR, the mixture was neutralized with dilute hydrochloric acid, 174ml of toluene, 174ml of heptane and 174g of water were added, and the aqueous layer was removed. Then, the organic layer was washed with water until the aqueous layer became neutral, and the solvent was concentrated, thereby obtaining SO-1. By the way, by 29 Si-NMR confirmed that SO-1 was a mixture of cage structure, ladder structure and random structure.
The acid value contained in SO-1 was calculated by the following method. First, a 2ml microtiter plate was provided with a 0.1mol/L alcoholic potassium hydroxide solution (ethanol-based solution) (hereinafter referred to as "measurement solution") and a stirrer was prepared. Using a measuring cylinder, 50ml each of ethanol and toluene was accurately weighed, placed in a 200ml beaker, and stirred and mixed with a stirrer. 3 drops of phenolphthalein solution were added and blank titration (empty titration) was performed using the titration solution. To the solution after blank titration, 20g of a sample was added, and the mixture was stirred and mixed with a stirrer. Further, 3 drops of phenolphthalein solution were added, and the sample was titrated with a titration solution to obtain a titration amount. The method for calculating the acid value is calculated based on the following formula.
Acid value (mgKOH/g) =titration amount (ml) ×titration solution f×5.6 ≡sample amount (g)
Here, f represents a factor of a titration solution obtained with a standard hydrochloric acid solution. The N/10 potassium hydroxide alcoholic solution used in the above method had f of 0.094. The amount of the sample is the weight of the silsesquioxane contained in the sample.
The weight average molecular weight Mw of SO-1 is determined by Gel Permeation Chromatography (GPC). As the apparatus, a liquid chromatography apparatus (manufactured by Waters corporation, japan) was used. As the column, 3 Shodex GPC KF-802 (exclusion limit molecular weight: 5000, manufactured by Showa Denko Co., ltd.) and Shodex GPC GPC KF802.5 (exclusion limit molecular weight: 20000, manufactured by Showa Denko Co., ltd.) were used in series.
Further, the measurement was performed at a flow rate of 1 ml/min and a temperature of 40℃using tetrahydrofuran as a developing solution. The weight average molecular weight of the standard sample was determined by comparison and conversion using polystyrene.
(B3) Composition of the components
(B31) Composition of the components
Component (B31 a)
9G: polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain 9, average molecular weight 536).
14G: polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain 14, average molecular weight 736).
A-400: polyethylene glycol diacrylate (average chain length of ethylene glycol chain 9, average molecular weight 508).
Component (B31B)
BPE800:2, 2-bis [4- (methacryloxypolyethoxy) phenyl ] propane (c+d=10, average molecular weight 804).
Component (B31 c)
APC56: polycarbonate diol (average molecular weight 1000) obtained by phosgenation of pentamethylene diol and hexamethylene diol
(B32) Composition of the components
Component (B32 a)
TMPT; trimethylolpropane trimethacrylate.
D-TMP; di (trimethylol) propane tetraacrylate.
(B33) Composition of the components
TSL-1: gamma-methacryloxypropyl trimethoxysilane.
GMA: glycidyl methacrylate.
(C) Composition of the components
PC1: a compound of the formula
PC2: compounds represented by the following formula are synthesized by reference to the method described in WO 2019/013049
PC3: a compound represented by the following formula, wherein a photochromic compound is bonded to both ends of a polypropylene glycol chain having a molecular weight of 2000, and which is synthesized by the method described in WO2012/149599
PC4: a compound of the formula
/>
PC5: a compound of the formula
PC6: a compound of the formula
(D) Composition of the components
OC-1: xylene (boiling point 138 ℃, SP value 8.7).
OC-2: toluene (boiling point 111 ℃, SP value 8.8).
OC-3: ethyl acetate (boiling point 80 ℃, SP value 9.1).
OC-4: propylene glycol monoethyl ether (boiling point 120 ℃, SP value 9.1).
(E) Component (E1) component
HALS-2:1,2, 6, -pentamethyl-4-piperidinyl methacrylate (molecular weight 239). In the formula (X), R 100 R is R 300 A compound which is methyl and t, u and v are 0.
HALS-3: a hindered amine (molecular weight 370) represented by the following formula (HALS-3)
It should be noted that HALS-3 was prepared by the following method.
A200 mL four-necked flask was equipped with stirring vanes, a thermometer and a dropping funnel, and the flask was charged with
1,2, 6-pentamethyl-4-hydroxypiperidine; 17.0g (0.1 mol),
dibutyl tin dilaurate; 7.4mg of the total weight of the powder,
dibutyl hydroxy toluene; 6.1g (0.05 mol),
dehydrating toluene; 60mL.
The mixture was heated to 60℃and 19.9g (0.1 mol) of 2- (2-methacryloyloxyethoxy) ethyl isocyanate were added little by little. Stirring at 60-65 deg.c for 1 hr. Then, the mixture was washed 3 times with 50mL of water, and extracted with toluene. After drying over magnesium sulfate, the solvent was distilled off. Neutral alumina column { developing solvent: chloroform/ethyl acetate=3/1 (v/v) } the resulting white solid was purified to obtain 36.3g of a white solid.
The elemental analysis values of the product were C65.09%, H9.75%, N7.70%, O17.47%. This value is taken as C 20 H 35 N 2 Ο 4 Is extremely consistent with the calculated values of C65.19%, H9.85%, N7.60% and O17.37%.
Further, as a result of measurement of nuclear magnetic resonance spectrum of proton, a peak of 32 proton parts was observed at 1 to 5ppm, and a peak of 2 proton parts based on methacryloyl group and a peak of 1 proton part based on hydrogen atom at 4 th position of piperidinyl group were observed at 5 to 7 ppm.
In summary, the compounds represented by the formula (HALS-3) were confirmed. The yield thereof was found to be 92%.
(E2) Composition of the components
HALS-1: bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate (molecular weight 508). In the formula (Y), R 500 R is R 600 A compound which is methyl and W is 8.
Other additives
Polymerization initiator
CGI1: phenyl bis (2, 4, 6-trimethylbenzoyl) -phosphine oxide (trade name: omnirad819, manufactured by IGM Co.).
CGI2: 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad184, manufactured by IGM Co.).
Stabilizing agent
HP: ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] (manufactured by CibaSpecialty Chemicals inc., irganox 245).
Leveling agent
L7001: (trade name: L7001, manufactured by Dow Corning Toray Co.Ltd.).
ER-10: (trade name: ER-10, manufactured by ADEKA Co., ltd.)
NE-10: (trade name: NE-10, manufactured by ADEKA Co., ltd.)
Catalyst
CA-1: dimethylphenylphosphine
Example 1 >
(production of photochromic curable composition)
First, each component was prepared according to the following formulation.
(A) The components are as follows: a1 0.1 parts by mass.
(B1) The components are as follows: RX-1 3 parts by mass.
(B2) The components are as follows: SO-1 0.1 mass portion.
(B31 a) component: 9G 40 parts by mass.
(B31 a) component: a-400 parts by mass.
(B32 a) component: 25 parts of TMPT.
(B33) The components are as follows: TSL-1.9 parts by mass, GMA 1 part by mass.
(C) The components are as follows: PC1 2 parts by mass.
(E) The components are as follows: (E1) a component; HALS-2.5 parts by mass of a component (E2); HALS-1 1 parts by mass.
(polymerization initiator); 0.3 part by mass of CGI-1 and 0.3 part by mass of CGI-2.
(stabilizers); HP 1 parts by mass.
Then, the total amount of the compounds belonging to the component (B) is mixed, and then the component (C), the component (E) and other additives are mixed therein to obtain a mixture. The component (A) is further mixed with the mixture to obtain a photochromic curable composition.
(production of photochromic laminate)
Using the photochromic curable composition obtained by the above method, a photochromic laminate was produced by a coating method. Specifically, first, as an optical base material, a thiocarbamate plastic lens having a center thickness of 2mm and a refractive index of 1.60 was prepared. As the thiocarbamate plastic lens, a lens was used which was subjected to alkali etching at 50 ℃ for 5 minutes using a 5% sodium hydroxide aqueous solution, and then sufficiently washed with distilled water.
Next, the coating liquid was applied on the surface of the above-mentioned plastic lens by a spin coater (1H-DX 2, manufactured by MIKASA) at a rotation speed of 70rpm for 15 seconds, followed by 1000rpm for 10 seconds, to obtain a polyurethane resin layer of 6. Mu.m. As the coating liquid, a moisture-curable primer liquid containing a precursor of a moisture-curable urethane resin and a solvent is used. The solvent contained toluene (boiling point 111 ℃, SP value 8.8) and ethyl acetate (boiling point 77 ℃, SP value 9.0), and the amount of ethyl acetate was 185 parts by mass with respect to 100 parts by mass of toluene.
Then, about 2g of the photochromic curable composition obtained above was applied to the urethane resin layer by spin coating to obtain a coating film having a film thickness of 40. Mu.m. In spin coating, the lens is first rotated at 100rpm for 30 seconds to form a coating film, and then the rotational speed is increased to 900rpm, and the lens is further rotated for 5 to 15 seconds to remove the excess photochromic curable composition.
Then, a lens having a coating film of the photochromic curable composition formed thereon was subjected to a power of 200mW/cm in a nitrogen atmosphere 2 The metal halide lamp of (2) was irradiated with light for 90 seconds to cure the coating film. Then, the mixture was heated at 90℃for 1 hour to prepare a photochromic laminate having a photochromic resin layer. The same procedure was repeated to prepare 20 photochromic laminates.
Examples 2 to 18 and comparative examples 1 to 2 >, respectively
A photochromic curable composition and a photochromic laminate were produced in the same manner as in example 1, except that the compounding of each component and the power of the metal halide lamp were changed as described in table 1 or table 2.
Examples 19 to 55 >
A photochromic curable composition and a photochromic laminate were produced in the same manner as in example 1, except that the compounding of each component and the power of the metal halide lamp were changed as described in table 4, table 5 or table 6. In addition, when the catalyst is added, the catalyst is added before the photochromic laminate is manufactured.
< evaluation method >)
(photochromic Properties)
The photochromic laminated bodies obtained in examples and comparative examples were used as samples, and the optical beam intensity at the surface of a photochromic optical article was 365 nm=2.4 mW/cm at 23.+ -. 1 ℃ via an air mass filter (manufactured by Corning Incorporated) 2 、245nm＝24μW/cm 2 The resultant was irradiated with a xenon lamp L-2480 (300W) SHL-100 (manufactured by Hamamatsu Photonics K.K.) for 300 seconds to develop a color, and the following maximum absorption wavelength, color development concentration and color fading rate were measured. The measurement was performed using 20 photochromic laminates, and the average value was calculated. The average values are shown in Table 3, table 7 or Table 8.
Maximum absorption wavelength (λmax):
the maximum absorption wavelength after color development was determined by a spectrophotometer (instantaneous multichannel photodetector MCPD 3000) manufactured by Otsuka electronics corporation. The maximum absorption wavelength is related to the color tone at the time of color development.
Color development concentration { ε (300) - ε (0) }:
the difference between the absorbance { ε (300) } after 300 seconds of light irradiation and the absorbance ε (0) before light irradiation at the maximum absorption wavelength. The higher the value, the more excellent the photochromic property.
Fade rate [ t1/2 (sec.):
when the irradiation of light was stopped after 300 seconds of irradiation of light, the absorbance at the maximum absorption wavelength of the sample was reduced to 1/2 of { ε (300) } ε (0). The shorter the time, the more excellent the photochromic property.
(repetition durability)
To evaluate the color development of photochromic compounds based on light irradiationThe durability was repeated, and the following degradation-promoting test was performed. First, the obtained photochromic laminate was subjected to degradation promotion for 200 hours by Xenon weather meter { manufactured by Suga testing machine Co., ltd., X25 }. Before and after the degradation, the color development concentration was evaluated, and the color development concentration (a 0 ) Color development concentration after test (A) 200 )。
Based on the measurement result, a target residual rate of the repetition durability is calculated. The results are shown in Table 3, table 6 or Table 7.
Residual ratio (%) = { (a) 200 /A 0 )×100}
In the method, in the process of the invention,
A 0 for the color development concentration before the test,
A 200 the color development concentration after the test.
Further, a value of yellowing factor (. DELTA.YI) was obtained using a colorimeter { Suga laboratory Co., ltd., SM-4 }.
ΔYI＝YI 200 -YI 0
In the method, in the process of the invention,
YI 200 to perform YI after 200 hours of degradation promotion,
YI 0 to promote YI before deterioration.
The higher the residual ratio, the smaller the yellowing, the higher the repetition durability, and the more excellent the photochromic property.
(appearance evaluation)
First, a protective film was attached to the photochromic resin layer of the photochromic laminate obtained in examples and comparative examples. The thickness of the adhesive layer in the protective film was 0.1mm, and an acrylic adhesive was used. Then, the photochromic laminate to which the protective film was attached was heated at a temperature of 70℃for 1 hour.
After the protective film was peeled off from the heated photochromic laminate, the exposed photochromic resin layer was observed by an optical microscope and an illumination device (QC X75, manufactured by Valvetronix corporation) to evaluate the appearance. Next, a protective film was again attached to the photochromic resin layer, and the protective film was further heated at a temperature of 70 ℃. After the protective film was peeled off from the photochromic laminate heated for a total of 2 hours, the exposed photochromic resin layer was observed again by using an optical microscope and an illumination device, and appearance was evaluated. The appearance evaluation was performed using all 20 sheets of photochromic laminate.
When the appearance was good after heating for 2 hours, this means that even when the protective film was attached for a long period of time, a photochromic laminate excellent in appearance could be obtained after peeling off the protective film.
The appearance was evaluated by 4 methods of smoothness (appearance), cracks, cloudiness, and wrinkle failure. The evaluation criteria are as follows. The results are shown in Table 3, table 7 or Table 8.
Smoothness of
A: the 20 photochromic laminates were all uniform in surface and no irregularities were observed at all.
B: of the 20 photochromic laminates, 1 or more photochromic laminate with fine irregularities visible on the surface was present, and the rest of the photochromic laminate was evaluated as a above.
C: of the 20 photochromic laminates, there were 1 or more photochromic laminates with Xu Aotu visible on the surface, and the rest were evaluated as a or B.
D: of the 20 photochromic laminates, 1 or more had a surface with irregularities partially visible, and the rest of the photochromic laminates were any of the above evaluations a to C.
E: among 20 photochromic laminates, there were 1 or more photochromic laminates with irregularities visible on the entire surface.
Cracking of
A: the 20 photochromic laminates were all uniform in surface and no cracks were visible at all.
B: of the 20 photochromic laminates, 1 or more photochromic laminate had very few microcracks visible on the surface, and the rest of the photochromic laminate was evaluated as a.
C: of the 20 photochromic laminates, there were 1 or more photochromic laminates with Xu Liewen visible on the surface, and the rest were evaluated as a or B.
D: of the 20 photochromic laminates, 1 or more had a surface with a part of cracks visible, and the rest of the photochromic laminates were any of the above evaluations a to C.
E: among 20 photochromic laminates, there were 1 or more photochromic laminates with cracks visible on the entire surface.
White turbidity
A: the 20 photochromic laminates were all uniform in surface and no cloudiness was seen at all.
B: of the 20 photochromic laminates, 1 or more photochromic laminate with little visible fine white turbidity was present, and the rest of the photochromic laminate was evaluated as a.
C: of the 20 photochromic laminates, there were 1 or more photochromic laminate of Xu Baizhuo visible, and the rest of the photochromic laminates were evaluated as a or B.
D: of the 20 photochromic laminates, 1 or more photochromic laminate with a part of white turbidity was found, and the rest of the photochromic laminates were any of the above evaluations a to C.
E: of the 20 photochromic laminates, 1 or more had a total visible white turbidity.
Poor wrinkles
A: the 20 sheets of photochromic laminate were all completely free from wrinkles in the photochromic resin layer, i.e., fine lines or streaks like wrinkles.
B: among 20 photochromic laminates, there were 1 or more photochromic laminates in which very few fine wrinkles were poor in the photochromic resin layer, and the rest of the photochromic laminates were evaluated as a above.
C: of the 20 photochromic laminates, 1 or more photochromic laminate had slight wrinkles and the rest were evaluated as a or B.
D: among 20 photochromic laminates, there were 1 or more photochromic laminates in which wrinkles were partially visible in the photochromic resin layer, and the rest of the photochromic laminates were any of the above evaluations a to C.
E: among 20 photochromic laminates, there were 1 or more photochromic laminates in which wrinkles were poor in the entire photochromic resin layer.
(yield)
Among 20 photochromic optical articles, the number of articles having no appearance defect was counted, and the number of articles divided by 20 was calculated as the yield. The results are shown in Table 3, table 6 or Table 7.
(adhesion)
The adhesion of the photochromic laminate was evaluated by the Cross cut test according to JISD-0202. That is, using a cutter, cuts were formed at 1mm intervals on the surface of the resulting photochromic laminate, and 100 grids were formed. A cellophane adhesive tape (nichiba co., ltd. Cellophane (registered trademark)) was strongly attached thereto, and then the number of remaining meshes on the photochromic optical article was calculated after one-time pulling and peeling from the surface in the 90 ° direction. The test was performed using 20 pieces of photochromic laminate, and the average value thereof was taken as the number of remaining grids. The number of remaining cells is shown in table 3, table 7 or table 8 as an indicator of adhesion.
(Vickers hardness)
The vickers hardness of the photochromic laminate was measured using a micro vickers hardness tester PMT-X7A (manufactured by Matsuzawa co., ltd.). The indenter was measured using a diamond indenter having a square pyramid shape, under a load of 10gf and a holding time of 30 seconds. The measurement was performed 4 times in total, and the measurement results were shown as an average value of 3 times in total except for the 1 st time value having a large measurement error. The test was performed using 20 pieces of photochromic laminate, and the average value thereof was taken as the vickers hardness. The results are shown in Table 3, table 7 or Table 8.
(contact angle)
First, ethylene glycol (2.0. Mu.l) was dropped onto the photochromic resin layer of the photochromic laminate to form droplets. The contact angle of the droplet was measured 5 times after 5 seconds from the dropping using an automatic contact angle meter DM500 (manufactured by Kyowa Kagaku Co., ltd.) to obtain an average value. The test was performed using 20 pieces of photochromic laminate, and the average value thereof was used as the contact angle. The results are shown in Table 3, table 7 or Table 8.
(SP value difference)
The difference between the SP value of the photochromic curable composition and the SP value of the adhesive of the protective film was calculated by the following method.
First, the SP values of the photochromic curable compositions obtained in examples and comparative examples were calculated by the turbidity titration method. Specifically, 2.0g of the photochromic curable composition was dissolved in 10ml of acetone. The obtained photochromic curable composition solution was titrated with deionized water and n-hexane, and the amount of turbidity of the solution was calculated. From the obtained values, SP values were calculated using the following formulas.
SP value= ((VH) 1/2 ×δH+(VL) 1/2 ×δL)/((VH) 1/2 +(VL) 1/2 )。
VH＝H/(S+H)。
VL＝L/(S+L)。
δH＝A×S/(S+H)+B×H(S+H)。
δL＝A×S/(S+L)+C×H(S+L)。
H: n-hexane was added dropwise (ml).
L: deionized water titration amount (ml).
VH: hexane volume ratio.
VD: volume ratio of deionized water.
S: acetone dosage (ml).
A: SP value of acetone.
B: SP value of n-hexane.
C: SP value of deionized water.
Next, the SP value of the adhesive of the protective film was calculated by the same method as described above. Further, the SP value of the adhesive of the protective film was removed from the SP value of the photochromic curable composition, resulting in a poor SP value. The absolute value of the difference is shown in table 3, table 7 or table 8 as the SP value difference.
(turbidity)
In order to evaluate the turbidity of the surface of the photochromic composition during long-term storage, the following storage acceleration test was performed. That is, the resulting photochromic laminate was left to stand in a constant temperature and humidity tank at 60℃and 98% RH for 24 hours. The difference in HAZE (Δhaze) values before and after the test was obtained using a HAZE meter. The results are shown in Table 3, table 7 or Table 8.
Delta HAZE e=haze 24-HAZE0
In the method, in the process of the invention,
HAZE 24 the haze after 24 hours is indicated,
HAZE 0 indicating the haze before being placed in a constant temperature and humidity tank.
TABLE 1
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TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
Description of the reference numerals
1: polyrotaxane
2: axis molecule
3: cyclic molecules
4: bulky terminal groups
5: side chain

Claims (11)

1. A photochromic curable composition comprising:
(A) A siloxane having an acyclic polysiloxane bond, and at least one of a radical polymerizable group and a group reactive with the radical polymerizable group;
(B) A radically polymerizable monomer component; and
(C) Photochromic compounds.
2. The photochromic curable composition according to claim 1, wherein the amount of the siloxane is 0.01 to 10 parts by mass based on 100 parts by mass of the radically polymerizable monomer component.
3. The photochromic curable composition according to claim 1 or 2, wherein the siloxane comprises a compound represented by the following formula (8):
in the above-mentioned formula (8),
n is a number of 0 to 20,
o is a number from 0 to 20,
p is a number of 0 to 20,
R 18 、R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 、R 28 r is R 29 Respectively hydrogen atom, alkyl group with 1-20 carbon atoms, alkoxy group with 1-20 carbon atoms, phenyl group, - (CH) 2 ) α OR 30 、-(CH 2 CH 2 O) α R 30 、-(CH(CH 3 )CH 2 O) α R 30 、-(CH 2 CH(CH 3 )O) α R 30 、-(CH 2 ) q O-(CH 2 CH 2 O) r R 30 -、-(CH 2 ) q O-(CH(CH 3 )CH 2 O) r R 30 、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r R 30 、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r R 30 、-(CH 2 CH(CH 3 )O) q -(CH 2 CH 2 O) r R 30 、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s R 30 、-(CH 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s R 30 、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s R 30 、-(CH 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s -(CH 2 CH 2 O) z R 30 Acryl, methacryl, vinyl, thiol, amino, -R 31 NH 2 An epoxy group, a group represented by the following formula (9) or a group represented by the following formula (10),
R 30 is hydrogen atom, methyl, ethyl, n-propyl or isopropyl,
R 31 is alkylene or- (CH) having 1 to 20 carbon atoms 2 ) α O-，
Wherein R is 18 ～R 29 At least one of them is an acryl, methacryl, vinyl, thiol, amino, -R 31 NH 2 An epoxy group, a group represented by the following formula (9) or a group represented by the following formula (10),
in the formula (9), R 32 Is an alkylene group having 1 to 20 carbon atoms, - (CH) 2 ) α O-、-(CH 2 CH 2 O) α -or- (CH) 2 CH(CH 3 )O) α -，
R 33 Is a hydrogen atom or a methyl group,
in the formula (10), R 34 Is an oxygen atom, - (CH) 2 ) α O-、-(CH 2 CH 2 O) α -、-(CH(CH 3 )CH 2 O) α -、-(CH 2 CH(CH 3 )O) α -、-(CH 2 ) q O-(CH 2 CH 2 O) r -、-(CH 2 ) q O-(CH(CH 3 )CH 2 O) r -、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r -、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r -、-(CH 2 CH(CH 3 )O) q -(CH 2 CH 2 O) r -、-(CH 2 CH 2 O) q -(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s -、-(CH 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s -、-(CH 2 ) q O-(CH 2 CH(CH 3 )O) r -(CH 2 CH 2 O) s -or- (CH) 2 ) q O-(CH 2 CH 2 O) r -(CH 2 CH(CH 3 )O) s -(CH 2 CH 2 O) z -，
R 35 Is a hydrogen atom or a methyl group,
in the formula (8), the formula (9) and the formula (10), α is a number of 1 to 20, q, r, s and z are a number of 0 to 20, q+r is a number of 1 to 40, q+r+s is a number of 1 to 60, and q+r+s+z is a number of 1 to 80, respectively.
4. A photochromic curable composition according to any one of claims 1 to 3, wherein the free radically polymerizable groups of the siloxane and groups reactive with free radically polymerizable groups comprise (meth) acryl groups.
5. The photochromic curable composition according to any one of claims 1 to 4, wherein the radically polymerizable monomer component comprises a polyrotaxane compound having a radically polymerizable group.
6. The photochromic curable composition according to any one of claims 1 to 5, wherein the radically polymerizable monomer component comprises a silsesquioxane having a (meth) acryloyl group having 2 or more functions.
7. The photochromic curable composition of any one of claims 1-6, further comprising a reactive hindered amine compound having 1 or more reactive groups selected from at least 1 of the group consisting of free radically polymerizable groups and groups reactive with free radically polymerizable groups.
8. The photochromic curable composition of any one of claims 1 to 7, further comprising a non-reactive hindered amine compound having no free radically polymerizable groups and groups reactive with free radically polymerizable groups.
9. The photochromic curable composition according to any one of claims 1 to 8, further comprising an organic compound having a boiling point of 80 ℃ or more and 200 ℃ or less and an SP value of 8.0 or more and 10.0 or less of hildebrand.
10. A photochromic stack comprising:
an optical substrate,
A photochromic resin layer which is a cured product of the photochromic curable composition according to any one of claims 1 to 9, and
and a polyurethane resin layer located between the optical substrate and the photochromic resin layer.
11. A method of manufacturing a photochromic stack comprising: a step of forming a polyurethane resin layer by applying a coating liquid containing at least 1 compound selected from the group consisting of polyurethane resins and precursors of moisture-curable urethane resins, and a solvent having a boiling point of 70 ℃ or higher and an SP value of 8.0 or higher, on one surface of an optical substrate and removing the solvent from the coating film; and
A step of applying the photochromic curable composition according to any one of claims 1 to 9 to the urethane resin layer, and curing the coating film to form a photochromic resin layer.
CN202280020016.1A 2021-03-08 2022-03-08 Photochromic curable composition, photochromic laminate, and method for producing same Pending CN116940871A (en)

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