JP2011153179A - Material composition and optical element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical material composition having a high refractive index, a small Abbe's number, and heat resistance and an optical element. <P>SOLUTION: The material composition includes a (meth)acryloyloxy alkylcarbazole (A) represented by chemical formula 1 (wherein R<SP>1</SP>is hydrogen or a methyl group and R<SP>2</SP>is a 1-3C alkylene group) and a polymerizable compound (B) having a biphenyl structure, a bisphenol A structure, a fluorene structure or a naphthalene structure and the optical element is composed of a cured product of the material composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an optical material composition suitable for forming an optical element and an optical element using the material composition. In particular, the present invention relates to an optical element material composition having high refractive index and high dispersion and excellent heat resistance, and an optical element using the material composition.

  As an imaging module, a camera, a video camera or a camera-equipped mobile phone, a videophone or a camera door phone, a security monitoring camera, and the like are known. In recent years, reduction in size and weight and cost of optical systems used in such imaging modules have become major issues. Since these optical systems are small, it is difficult to use a plurality of lenses. For this reason, an aspherical lens having a high refractive index is frequently used so that various optical aberrations can be corrected and this can be performed with a small number of lenses.

  As a high refractive index material composition, a curable material composition including a polymer composed of a radically polymerizable compound having a carbazole skeleton and a radical reactive monomer having a plurality of aromatic rings and a molecular weight of 550 or less has been proposed. (For example, refer to Patent Document 1), a refractive index nD of 1.60 or more is realized.

JP 2009-51972 A

However, when correcting chromatic aberration unlike other aberrations, the material composition is required not only to have a high refractive index but also to have a high dispersion by reducing the Abbe number.
In the material composition shown in Patent Document 1, no consideration is given to correction of chromatic aberration by reducing the Abbe number. Furthermore, the glass transition temperature of the material composition shown in Patent Document 1 is about 50 to 80 ° C. and does not satisfy the required heat resistance, and the temperature of the optical surface of the optical element varies depending on the temperature near the glass transition temperature. The shape changes greatly. For this reason, there is a problem in the stability of optical quality. The present invention has been made in view of such conventional problems, and provides an optical material composition having a small Abbe number and heat resistance while having a high refractive index, and an optical element using the same. This is the issue.

  The present inventors have disclosed a material composition comprising a compound of acryloyloxyalkylcarbazole or methacryloyloxyalkylcarbazole and a polymerizable compound having at least one structure selected from a biphenyl structure, a bisphenol A structure, a fluorene structure and a naphthalene structure in the molecule. It was found that an optical element having a high refractive index and high dispersion and excellent heat resistance can be obtained from the product.

  That is, the first aspect of the present invention includes (meth) acryloyloxyalkylcarbazole (A) represented by Chemical Formula 1 and at least one structure selected from a biphenyl structure, a bisphenol A structure, a fluorene structure, and a naphthalene structure in the molecule. The material composition containing the polymeric compound (B) which has is provided.

Ｒ１は、水素またはメチル基を表し、Ｒ２は、炭素数１以上３以下のアルキレン基を表す。

R1 represents hydrogen or a methyl group, and R2 represents an alkylene group having 1 to 3 carbon atoms.

Moreover, it is said material composition containing a polymerization initiator (C).
Moreover, it is the said material composition which further contains the polymeric compound (D) which has a 2 or more polymerizable vinyl group in a molecule | numerator.

  In the material composition, the polymerizable compound (B) is at least one selected from the group of compounds represented by Chemical Formulas 2, 3, 4, and 5.

Ｒ３はラジカル重合性官能基を有する有機基、Ｒ４は水素またはアルキル基またはラジカル重合性官能基を有する有機基を表す。

R3 represents an organic group having a radically polymerizable functional group, and R4 represents hydrogen, an alkyl group, or an organic group having a radically polymerizable functional group.

Ｒ５は水素またはメチル基を、Ａは、直接結合または、１個から３個のメチレン基を表す。

R5 represents hydrogen or a methyl group, and A represents a direct bond or 1 to 3 methylene groups.

Ｒ７はラジカル重合性官能基を有する有機基、Ｒ８は水素またはアルキル基またはラジカル重合性官能基を有する有機基を表す。

R7 represents an organic group having a radical polymerizable functional group, and R8 represents a hydrogen, an alkyl group or an organic group having a radical polymerizable functional group.

Ｒ９はラジカル重合性官能基を有する有機基、Ｒ１０は水素またはアルキル基またはラジカル重合性官能基を有する有機基を示す。

R9 represents an organic group having a radically polymerizable functional group, and R10 represents hydrogen, an alkyl group or an organic group having a radically polymerizable functional group.

Moreover, the 2nd aspect of this invention is the said optical element which is the hardened | cured material of one of the said material compositions.
The present invention provides an optical element comprising a cured product of the material composition, or a composite optical element in which a cured product of the material composition is laminated on the surface of an optical substrate.

  The present invention can provide a material composition useful for downsizing an optical system and correcting chromatic aberration. In addition, an optical element having excellent processability can be obtained.

It is a figure which shows an example of the shaping | molding apparatus which uses the optical element comprised only from the hardened | cured material which superposed | polymerized the material composition of this invention for shaping | molding. It is a figure which shows an example of a composite type optical element. It is a figure which shows an example of the manufacturing apparatus of a composite type optical element. It is a figure which shows the spreading state of the material composition of this invention.

In order to solve the above-mentioned problems, the material composition of the present invention comprises acryloyloxyalkylcarbazole or methacryloyloxyalkylcarbazole (hereinafter referred to as (meth) acryloyloxyalkylcarbazole) which is the compound (A) represented by the chemical formula 1. And a polymerizable compound (B) having at least one structure selected from a biphenyl structure, a bisphenol A structure, a fluorene structure, and a naphthalene structure in the molecule as an essential component.
(Meth) acryloyloxyalkylcarbazole is used as a main component of the material composition of the present invention, and its cured product is a polymerizable compound exhibiting a high refractive index and high dispersion, and constitutes an optical element that corrects chromatic aberration. It is a very useful component for making a material composition.

Examples of the compound (A) include acryloyloxymethyl carbazole, methacryloyloxymethyl carbazole, acryloyloxyethyl carbazole, methacryloyloxyethyl carbazole, acryloyloxypropyl carbazole, and methacryloyloxypropyl carbazole. These carbazole compounds may be used singly or as a mixture of a plurality of types. Also, in Formula 1, the acrylate in which R1 is hydrogen is higher in refraction than the methacrylate in which R1 is a methyl group. High dispersion and excellent curability. In the chemical formula 1, when the carbon number of R2 is small, the refractive index becomes high dispersion and the cured product is fragile.
In addition, since the compound (A) is solid at a temperature near room temperature, which is an atmospheric temperature of a general production process, it is difficult to produce an optical element alone at a temperature near room temperature. Furthermore, a single cured product is very fragile, and there is a problem that deformation and cracking occur due to a temperature change in a temperature range from a low temperature of about −40 ° C. to a high temperature of about 80 ° C.

Therefore, the content of the compound (A) in the resin component in the material composition of the present invention is preferably 39 to 95% by mass. If the blending ratio is less than 39% by mass, a sufficiently high refractive index and high dispersion cannot be obtained, and if it exceeds 95% by mass, deformation and cracking tend to occur when subjected to a temperature cycle. Moreover, when content of (A) is 50-95 mass%, it is still more preferable.
The polymerizable compound (B) is a compound having in the molecule at least one structure selected from a biphenyl structure, a bisphenol A structure, a fluorene structure, and a naphthalene structure, and further having at least one polymerizable functional group. And (meth) acryloyloxyalkylcarbazole, which is excellent in solubility, and is capable of forming a copolymer with compound (A) upon polymerization.

  The melting point of the polymerizable compound (B) is more preferably 80 ° C. or lower. If the melting point is 80 ° C. or lower, the material composition can be made into a liquid that can be processed in the temperature range from about room temperature to about 70 ° C., which is the atmospheric temperature in the process of processing into an optical element. If the melting point exceeds 80 ° C., the material composition must be kept at 70 ° C. or higher until the material composition is cured in the process of processing into an optical element, which is not preferable from the viewpoint of workability.

  The polymerizable compound having a biphenyl structure is represented by the following chemical formula 2. In the formula, either or both of R3 and R4 are radical polymerizable functional groups. The radical polymerizable functional group is a vinyl group, an allyl group, an acryloyl group or a methacryloyl group, and a cured product of the material composition forms a copolymer with the (meth) acryloyloxyalkylcarbazole which is the compound (A). Is a functional group capable of

ただし、Ｒ３はラジカル重合性官能基を有する有機基、Ｒ４は水素またはアルキル基またはラジカル重合性官能基を有する有機基を示す。

However, R3 represents an organic group having a radical polymerizable functional group, and R4 represents an organic group having hydrogen, an alkyl group or a radical polymerizable functional group.

Examples of the polymerizable compound having a biphenyl structure include diallyl diphenate, 2-phenylphenyl (meth) acrylate, and an ethylene oxide adduct of 2-phenylphenyl (meth) acrylate. From the viewpoint of the solubility of the (meth) acryloyloxyalkylcarbazole of the compound (A) and the workability of the optical element, it is particularly preferable to use diallyl diphenate.
The polymerizable compound having a fluorene structure is represented by the following chemical formula 3. In the formula, R5 represents hydrogen or a methyl group. A represents a direct bond or 1 to 3 methylene groups.
Since it has a (meth) acryloyl group, it can form a copolymer with (meth) acryloyloxyalkylcarbazole which is the compound (A). This component is a component necessary for making the material composition liquid at around room temperature, which is the atmospheric temperature in the process of processing into an optical element.
The cured product is a useful component for producing a high refractive index and high dispersion material composition having a high refractive index and a small Abbe number. In particular, compared to fluorene compounds having a bisphenyl structure such as 9,9-bis (4- (2-acryloyloxyethoxy) phenyl) fluorene, it has a higher refractive index and a lower viscosity at the time of processing, so it has an advantage of excellent workability. There is.

Further, in the chemical formula 3, the acrylate in which R5 is hydrogen has a higher refractive index and higher dispersion than the methacrylate in which R5 is a methyl group, and is excellent in curability.
Fluoryl (meth) acrylate directly bonded with a methacrylate group has a high refractive index, and as the number of methylene groups increases from 1 to 3, the refractive index decreases while flexibility increases and heat cycle characteristics improve. If the number of carbon atoms exceeds 3, it is difficult to obtain a cured product having a high refractive index and high dispersion, such being undesirable. In consideration of both high refractive index and heat cycle characteristics, n = 1 or 2 is particularly preferable.

化学式３
Ｒ５は水素またはメチル基を、Ａは、直接結合または、１個から３個のメチレン基を表す。

Chemical formula 3
R5 represents hydrogen or a methyl group, and A represents a direct bond or 1 to 3 methylene groups.

Examples of the polymerizable compound having a fluorene structure include fluoryl acrylate, fluoronyl methacrylate, fluoronylmethyl acrylate, fluorylmethyl methacrylate, fluorylpropyl acrylate, and fluorylpropyl methacrylate.
The polymerizable compound having a naphthalene structure is represented by the following chemical formula 4. In the formula, either or both of R7 and R8 are radically polymerizable functional groups. The radical polymerizable functional group is a vinyl group, an allyl group, an acryloyl group or a methacryloyl group, and the cured product of the material composition can be a copolymer polymer with the (meth) acryloyloxyalkylcarbazole which is the compound (A). It is a functional group that can be.

Ｒ７はラジカル重合性官能基を有する有機基、Ｒ８は水素またはアルキル基またはラジカル重合性官能基を有する有機基を示す。

R7 represents an organic group having a radical polymerizable functional group, and R8 represents a hydrogen or alkyl group or an organic group having a radical polymerizable functional group.

  Examples of the polymerizable compound having a naphthalene structure include 1- (meth) acryloyloxynaphthalene, 1- (meth) acryloyloxy-4-methoxynaphthalene, 1- (meth) acryloyloxy-4-vinylnaphthalene, 1,4-di (Meth) acryloyloxynaphthalene, 2,6-di (meth) acryloyloxynaphthalene, 1- (meth) acryloyloxypolyalkoxynaphthalene, 1,4-di (meth) acryloyloxypolyalkoxynaphthalene, 2,6-di ( And (meth) acryloyloxypolyalkoxynaphthalene.

  The polymerizable compound having a bisphenol A structure is represented by Chemical Formula 5. At least one of R9 and R10 is a radical polymerizable functional group. The radical polymerizable functional group is, for example, a vinyl group, an allyl group, an acryloyl group or a methacryloyl group, and the cured product of the material composition is co-polymerized with the compound (A) (meth) acryloyloxyalkylcarbazole. It is a functional group that forms a coalescence.

Ｒ９はラジカル重合性官能基を有する有機基、Ｒ１０は水素またはアルキル基またはラジカル重合性官能基を有する有機基を意味する。

R9 represents an organic group having a radical polymerizable functional group, and R10 represents a hydrogen or alkyl group or an organic group having a radical polymerizable functional group.

Examples of the polymerizable compound having a bisphenol A structure include bisphenol A di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, bisphenol A propylene oxide modified di (meth) acrylate, and bisphenol A glycidyl di (meth) acrylate. be able to.
As the polymerizable compound (B), the compounds represented by the chemical formulas 2 to 5 described above may be used singly or as a mixture of a plurality of types.
The content of the polymerizable compound (B) in the material composition is 4 to 55% by mass. More preferably from 10 to 3 0% by weight. If it is less than 5% by mass, sufficient heat resistance cannot be obtained, so that deformation and cracking are likely to occur during temperature changes. On the other hand, when it exceeds 55% by mass, it is difficult to obtain a material composition having a sufficiently high refractive index and high dispersion.

  The material composition of the present invention may further contain a polymerization initiator (C). By including the polymerization initiator (C), curing of the resin can be facilitated. Moreover, as a polymerization initiator (C), both a thermal polymerization initiator and a photoinitiator can be used. Among these, the use of a photopolymerization initiator is preferable because the resin can be cured by ultraviolet light irradiation for a relatively short time and the surface accuracy of the resin can be easily secured.

  Photoinitiators include 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl clasphine oxide, benzophenone and Benzophenone derivatives, benzyl and benzyl derivatives, benzoin and benzoin derivatives, alkyl benzoylbenzoate, bis (4-dialkylaminophenyl) ketone, benzoin alkyl ether, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, alkoxyacetophenone, Examples thereof include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthone and thioxanthone derivatives, and trimethylbenzoyl-diphenyl-phosphine oxide. These polymerization initiators may be used alone or in combination of two or more.

The content of the polymerization initiator (C) is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the material composition excluding the polymerization initiator. More preferably, it is 1-2 mass parts. When the content is 0.1 parts by mass, a material composition having sufficient curability cannot be obtained, resulting in a cured product having a low degree of curing. On the other hand, when the amount exceeds 5 parts by mass, there is a problem that the transparency of the cured product is lowered or the light resistance is lowered.
Even when the polymerization initiator (C) is not contained, the curable resin composition of the present invention is based on radical polymerization by applying high energy radiation energy such as X-rays or electron beams, or thermal energy. Curing is possible.

The material composition of the present invention may further contain a polymerizable compound (D). The polymerizable compound (D) is a polymerizable compound other than the compound (B) having two or more polymerizable vinyl groups in the molecule.
The polymerizable vinyl group is a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group, and is a functional group that can be copolymerized with the compound (A) (meth) acryloyloxyalkylcarbazole and the compound (B). In addition to improving the heat resistance of the composition, it is a component for adjusting heat cycle characteristics and workability.

  Examples of the polymerizable compound having two or more polymerizable vinyl groups include aliphatic, alicyclic or aromatic di (meth) acrylate, tri (meth) acrylate or poly (meth) acrylate, polyester (meth) acrylate, Urethane (meth) acrylate and epoxy (meth) acrylate can be selected. Specifically, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, pentaerythritol tri (meth) Examples include acrylate, pentaerythritol tetra (meth) acrylate, butanediol (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol, and polyfunctional polyester (meth) acrylate. From the viewpoint of heat resistance and processability, trimethylolpropane tri (meth) acrylate or polyfunctional polyester acrylate is particularly preferred, and examples of materials that can be used in the present invention include Aronix M 7300K (manufactured by Toagosei Co., Ltd.).

  Since the polymerizable compound (D) has two or more polymerizable functional groups in the molecule, the degree of polymerization of the cured product of the material composition or the crosslinking density is increased, and the effect of improving the heat resistance is obtained. Moreover, the viscosity and melting | fusing point of a material composition can be adjusted to the range which is easy to process by mix | blending polymeric compound (D). On the other hand, the polymerizable compound (D) tends to have a lower refractive index and lower dispersion than the compound (A) and the polymerizable compound (B). The amount needs to be kept low. Therefore, the content of the polymerizable compound (D) is preferably 0 to 30% by mass. More preferably, it is 0-20 mass%. When it is more than 30% by mass, it is difficult to obtain a material composition having a high refractive index and high dispersion.

In addition to the above components, the material composition of the present invention may further contain a UV absorber or an antioxidant to improve durability.
The refractive index of the cured product of the material composition of the present invention preferably exceeds 1.60 in the refractive index nd at the d-line. More preferably, it is 1.61 or more. If the refractive index nd is lower than 1.60, the optical system cannot be sufficiently miniaturized, and the optical system and the lens become large. In order to correct chromatic aberration, the Abbe number νd is preferably less than 30. More preferably, it is less than 25. When the Abbe number νd exceeds 30, a sufficient effect for correcting chromatic aberration cannot be obtained. The Abbe number νd is a value calculated from the following equation 2.
νd = (nd−1) / (nF−nC) …… Equation 2
(However, nd, nC, and nF are refractive indexes for d-line, C-line, and F-line, respectively)

The optical element and composite optical element of the present invention will be described below with reference to the drawings.
FIG. 1 is a view showing an example of a molding apparatus for molding an optical element of the present invention.
In addition, the optical element of this invention is an optical element comprised only from the hardened | cured material which superposed | polymerized the optical material composition of this invention as mentioned above. The optical element molding apparatus 1 includes a cylindrical metal barrel mold 2, a metal upper mold 3 having a desired optical surface 3a, a lower mold 4 having a desired optical surface 4a and made of glass that transmits ultraviolet rays, A drive rod 5 for driving the upper die 3 up and down and a release cylinder 6 for releasing the cured optical element from the lower die 4 are provided. The cylindrical metal barrel mold 2 is provided with an inlet 7 for injecting a material composition and an outlet 8 for discharging an excess material composition.

The drive rod 5 slides up and down the upper die 3 in the metal barrel die 2 by a drive source (not shown). Further, the release cylinder 6 slides up and down in contact with the inner peripheral surface of the metal barrel mold 2. A molding chamber 9 for molding an optical element is formed by the optical surfaces of the upper mold 3 and the lower mold 4 and the inner peripheral surface of the metal barrel mold 2.
The optical element is molded by the following procedure. The metal upper mold 3 and the glass lower mold 4 are placed in the metal barrel mold 2 so that the optical surfaces 3a and 4a face each other. At this time, the upper die 3 is held at a predetermined height in the first stage by the drive rod 5. The predetermined height in the first stage is a height at which the upper mold 3 is located above the discharge port 8. By holding the upper die 3 at this height, a molding chamber 9 is formed.

Next, the material composition of the present invention containing a photopolymerization initiator is injected from the injection port 7 and filled into the molding chamber 9. At this time, if the inside of the molding chamber 9 is set to a negative pressure, it is possible to prevent entrainment of bubbles during injection of the material composition and air remaining in the molding chamber. When the material composition overflows from the discharge port 8, it is determined that the molding chamber 9 is filled, and the injection of the material composition is stopped.
The inlet 7 is closed, and the upper die 3 is pressed downward to the second stage height. At this time, an excessive material composition flows out from the discharge port 8. Next, the material composition is cured by irradiating ultraviolet rays from below the lower mold 4. In addition, although the ultraviolet irradiation device is arrange | positioned under the release cylinder 6, illustration is abbreviate | omitted. The upper mold 3 is gradually moved downward in accordance with the shrinkage accompanying the curing of the material composition. By lowering the upper mold 3 in conjunction with the shrinkage, the internal stress of the cured optical element can be reduced. After the material composition is sufficiently cured, the drive rod 5 is raised to release the upper mold 3. Next, the release cylinder 6 is moved upward to release the cured product from the lower mold 4. In this way, a cured product made of the material composition can be taken out as an optical element having a desired shape.

  In FIG. 1, a spherical lens is used if both of the optical surfaces 3a and 4a are spherical, and an aspheric lens is used if any of the optical surfaces 3a and 4a is aspheric. Alternatively, if both are diffractive surfaces, each diffractive lens can be manufactured as an optical element.

The composite optical element of the present invention is produced by curing the above-described material composition on the surface of the optical substrate, and laminating the optical substrate and a cured product of the material composition. be able to.
This composite optical element is a composite optical element in which the interface between the optical substrate and the cured product of the material composition is a spherical surface, an aspherical surface, a free-form surface, or a diffractive surface. As an optical base material used for the composite optical element, ordinary optical glass, optical resin, or transparent ceramic that does not cause problems such as chipping, surface discoloration, devitrification, or turbidity when processed into a desired shape is used. be able to. Examples of the optical glass include quartz, BK7 (SCHOOT), BACD11 (HOYA), BAL42, LAH53 (Ohara). Examples of optical resins include amorphous polyolefins such as Zeonex (Nippon Zeon), ARTON (JSR), Appel (Mitsui Chemicals), acrylic resins such as Acrypet (Mitsubishi Rayon) and Delpet (Asahi Kasei). it can.

The surface of the optical substrate is filled with the material composition of the present invention, and a mold is brought into contact with the upper surface so as to have a desired shape. The mold used at this time may be made of metal or glass. However, when the material composition is cured by irradiating ultraviolet rays from the opposite surface of the optical substrate, a glass mold is used. When a metal mold is used, the material composition is cured by irradiating ultraviolet rays from the side of the optical substrate.
By such a method, for example, a composite optical element as shown in FIG. 2 can be manufactured. In the composite optical element 10 shown in FIG. 2, a cured product 13 of the material composition is integrally formed on the surface of the optical substrate 11.

Hereinafter, a method for manufacturing the composite optical element will be described.
FIG. 3 is a diagram for explaining an example of a composite optical element manufacturing apparatus, and the left side of the optical axis shows a cross section. The composite optical element manufacturing apparatus 20 includes a support frame (not shown), a support base 21, a receiving portion 22, and a holding cylinder 23. The support base 21 is supported by a support frame. The receiving portion 22 has a cylindrical shape and is attached to the support base 21. A bearing 24 is provided in the receiving portion 22.

The holding cylinder 23 is attached to the receiving portion 22 via the bearing 24, and the holding cylinder 23 is rotatable with respect to the receiving portion 22 by the action of the bearing 24. In addition, the holding cylinder 23 is provided with an annular engagement edge 25 that receives the outer edge portion of the optical base material 11 at the upper part of the inner periphery thereof. In addition, a pulley 26 is formed in the lower part of the holding cylinder 23.
On the other hand, a motor 27 is fixed below the support base 21. A pulley 29 is attached to the drive shaft 28 of the motor 27. A belt 30 is wound around the pulley 29 and the pulley 26. Thus, a rotating mechanism for rotating the holding cylinder 23 is configured.

The bearing 24 is fixed by pressing rings 31 and 32, respectively. That is, the holding ring 31 is screwed with the screw portion 22 a of the receiving portion 22, and the holding ring 32 is screwed with the screw portion 23 a of the holding cylinder 23. Thereby, the bearing 24 can be fixed between the receiving portion 22 and the holding cylinder 23.
A support means 35 is provided above the support base 21. The support means 35 moves the upper mold 3 up and down, and the support column 36 of the support means 35 that supports the upper mold 3 at a desired position is fixed to the upper surface of the support base 21. A cylinder 37 is provided.
A cylinder rod 38 is attached to the cylinder 37. Further, the upper die 3 is attached to the tip of the cylinder rod 38.
Further, the upper mold 3 is supported so that the optical axis 39 of the optical base 11 and the axis of the upper mold 3 coincide with each other with the optical base 11 placed on the engaging edge 25 of the holding cylinder 23. ing.

A composite optical element manufacturing method using the composite optical element manufacturing apparatus described above will be described.
The optical substrate 11 made of a lens having desired optical characteristics is placed so as to be positioned by the engagement edge 25 of the holding cylinder 23. In addition, you may perform the coupling process for improving the adhesiveness of a material composition and the glass-made optical base material to the material composition formation surface of the surface 11a of the optical base material 11. FIG. Next, a required amount of the material composition 12 is discharged onto the surface 11a of the optical substrate 11 by a discharge means (not shown).

Next, the cylinder 35 is operated to lower the upper mold 3, and the optical surface 3 a of the upper mold 3 is brought into contact with the material composition 12 discharged onto the surface 11 a of the optical substrate 11. By continuing further lowering, the material composition 12 is spread into a predetermined shape.
Before spreading to a predetermined shape, the lowering of the upper mold 3 is stopped. In this state, the optical base 11 is rotated at least once by operating the motor 27 and rotating the holding cylinder 23.

FIG. 4 is a view showing a spread state of the material composition 12. The upper mold 3 is pressed against the material composition 12 placed on the surface 11a of the optical substrate 11 so that the optical axis 39 of the optical substrate 11 and the axis of the upper mold 3 coincide with each other, so that the optical substrate 11 side is Make at least one revolution. By doing in this way, the material composition 12 extends uniformly in the space between the surface 11a of the optical base material 11 and the upper mold | type 3, and a material composition layer is formed.
Thereafter, the cylinder 37 is operated again, and the upper die 3 is lowered again. Then, when the layer of the material composition 12 reaches a desired thickness and diameter (when it has a predetermined shape), the lowering of the upper mold 3 is stopped, and an ultraviolet irradiation device (illustrated) from the lower side of the optical substrate 11 is displayed. Do not irradiate with ultraviolet rays.
As a result, the material composition between the upper mold 3 and the optical substrate 11 is cured, and the cured product 13 of the material composition can be integrally formed on the surface 11 a of the optical substrate 11. At this time, an optical surface to which the optical surface 3a of the upper mold 3 is transferred is formed on the surface of the cured product 13 of the material composition. A composite optical element having a desired shape can be obtained by releasing the cured product from the optical surface 3a of the upper mold 3 from the surface of the cured product 13 of the material composition.

Example 1
Preparation of Material Composition 50% by mass of acryloyloxyethylcarbazole (AOECZ) as the compound (A), 49% by mass of 2-phenylphenyl acrylate (FFA) as the compound (B), and 2-hydroxy-2-yl as the compound (C) A material composition was prepared by uniformly stirring and mixing 1 mass% of methyl-1-phenyl-propan-1-one (HMPP) at 70 ° C.

(Production of cured product)
The material composition was molded into a size of 20 mm in diameter and 1 mm in thickness, irradiated with ultraviolet rays at a wavelength of 400 nm at an illuminance of 100 mW / cm ² for 100 seconds, and further heated at 80 ° C. for 1 hour to prepare a cured product. About the obtained hardened | cured material, the refractive index was measured and Abbe number (nu) d was calculated | required. The results are shown in Table 1.

(1) Measurement of refractive index The refractive index in d line, C line, and F line of the produced cured product was measured using a precision refractometer (KPR-200 manufactured by Shimadzu Device Manufacturing Co., Ltd.). The measurement environment was 20 ° C. and 60% RH.
(2) Calculation of Abbe number νd When the refractive indexes for the d-line, C-line, and F-line obtained by measurement are nd, nC, nF, and ng, respectively, the Abbe number νd was calculated from Equation 2 below. .
νd = (nd−1) / (nF−nC) …… Equation 2

(Production of composite optical elements)
A composite optical element having the shape shown in FIG. 2 was prepared using the molding apparatus shown in FIG. During the molding process, the material composition was heated to 70 ° C. and molded. In either case, ultraviolet light at a wavelength of 400 nm was irradiated for 100 seconds at an intensity of 100 mW / cm ² and further heated at 80 ° C. for 1 hour to produce a composite optical element having the shape shown in FIG.
In FIG. 2, the glass lens of the base material has a curvature radius R1 = 16 mm, a curvature radius R2 = 16 mm, L1 = 20 mm, and L3 = 5 mm. A composite optical element was fabricated on this substrate so that the curvature radius R3 = 26 mm and the aperture L2 = 16 mm. The fabricated composite optical element was evaluated for processability by the following method.

(5) Evaluation of heat resistance A heat resistance test was performed in which the prepared composite optical element was allowed to stand for 100 hours in an environment of 85 ° C and 85% RH, and then for 24 hours in an environment of 20 ° C and 60% RH. The cured surface of the material composition was visually observed to examine the appearance of cracks and cloudiness. If there was no problem, it was judged as “good”, and if there was a crack or white turbidity affecting the optical quality, it was judged as “bad”. Further, the radius of curvature was measured with a contact-type surface shape measuring instrument Foam Talysurf PGI Plus (Taylor Hobson). The amount of deformation with respect to the radius of curvature R3 at the initial stage of the heat resistance test was determined, and was judged “good” if the amount of deformation was within ± 2 microns, and “bad” otherwise.

Example 2
The compounding ratio of the compound (A) is changed to 70% by mass, the compound (B) is changed to 10% by mass of 2-phenylphenyl acrylate (FFA), 14% by mass of fluorenylmethyl methacrylate (FMMA), and bisphenol A represented by the chemical formula 6. A material composition was prepared in the same manner as in Example 1 except that the mixed material was changed to 5% by mass of ethylene oxide 2-mol addition dimethacrylate (BP2EM)). The results are shown in Table 1.

Example 3
The compounding ratio of the compound (A) is changed to 90% by mass, the compound (B) is changed to 8% by mass of diallyl diphenate (DAD), and 2-hydroxy-2-methyl-1-phenyl-propane is used as the compound (C). Except that the blending ratio of -1-one (HMPP) was changed to 2% by mass, a material composition was prepared in the same manner as in Example 1, and the characteristics were evaluated in the same manner as in Example 1. It is shown in 1.

Example 4
While changing the compounding ratio of the compound (A) to 60% by mass, the compound (B) is changed to 25% by mass of fluorylmethyl methacrylate (FMMA), 1-acryloyloxy-4 monomethoxynaphthalene (AOMN) 5% by mass, A material composition was prepared in the same manner as in Example 1 except that 9% by mass of trimethylolpropane triacrylate (TMPA) was used as the compound (D), and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5
The compounding ratio of the compound (A) is changed to 70% by mass, the compound (B) is changed to 10% by mass of fluorylmethyl methacrylate (FMMA), and further, as the compound (D), polyester acrylate (Aronix M7300K manufactured by Toa Gosei) 19 A material composition was prepared in the same manner as in Example 1 except that the mass% was used, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6
The compounding ratio of the compound (A) was changed to 45% by mass, the compounding ratio of the compound (B) was changed to 53% by mass, and the compound (C) was further changed to 2% by mass. A material composition was prepared, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 7
A material composition was prepared in the same manner as in Example 1 except that the compounding ratio of compound (A) was changed to 5% by mass and compound (B) was changed to 4% by mass of diallyl diphenate (DAD). The characteristics were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 8
The compounding ratio of the compound (A) is changed to 39% by mass, the compound (B) is changed to 55% by mass of diallyl diphenate (DAD), and further, as the compound (D), polyester acrylate (Aronix M7300K manufactured by Toa Gosei) 5% Except for the point using%, a material composition was prepared in the same manner as in Example 1, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
The compounding ratio of the compound (A) was changed to 50% by mass, the compound (B) was not compounded, and the compound (D) was used except that 49% by mass of polyester acrylate (Aronix M7300K manufactured by Toagosei Co., Ltd.) was used. A material composition was prepared in the same manner as in Example 1, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1. A material composition was prepared in the same manner as in Example 1 except that the blending ratio of the components in the material composition was changed as shown in Table 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 2
The compounding ratio of the compound (A) was changed to 50% by mass, the compound (B) was not compounded, and the compound (D) was used except that 49% by mass of trimethylolpropane triacrylate (TMPA) was used. A material composition was prepared in the same manner as in Example 1, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1. A material composition was prepared in the same manner as in Example 1 except that the blending ratio of the components in the material composition was changed as shown in Table 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

From the results shown in Table 1, the refractive index and Abbe number νd of the cured materials of the material compositions of the present invention in Examples 1 to 8 are 1.60 or more, both of which are in the preferred range, and the optical system is compact It was found to have a sufficient effect on the correction and correction of chromatic aberration. Moreover, it turned out that the optical element using the material composition of this invention in Examples 1-8 is excellent also in heat resistance.
On the other hand, in the material composition which does not contain the compound (B) as in Comparative Examples 1 and 2, the compatibility of the polyester acrylate of the compound (A) and the compound (D) or trimethylolpropane triacrylate is poor. Even if they are mixed, the material composition becomes cloudy, which is inappropriate as an optical material composition.

  According to the present invention, it is possible to obtain a material composition having sufficient characteristics for downsizing of an optical system and correction of chromatic aberration, and because it is excellent in workability, an optical element, particularly a composite optical element. Thus, it is possible to provide an optical element and a composite optical element that are easy to process, have a small size, and have excellent characteristics for correcting chromatic aberration.

  DESCRIPTION OF SYMBOLS 1 ... Composite-type optical element shaping | molding apparatus, 2 ... Metal cylinder type | mold, 3A ... Upper mold | type, 3B ... Lower mold | type, 3A1 ... Optical surface, 3B1 ... Optical surface, 4 ... Heating means, 5 ... Drive rod, 6 ... Mold release Cylinder, 7 ... injection port, 8 ... discharge port, 9 ... molding chamber, 10 ... composite optical element, 11 ... optical element, 11A ... surface, 12 ... material composition, 13 ... cured product, 21 ... support base, 23 ... Holding cylinder, 25 ... Engagement edge, 27 ... Motor, 35 ... Support means, 36 ... Support column, 37 ... Cylinder

Claims (6)

(Meth) acryloyloxyalkylcarbazole (A) represented by Chemical Formula 1 and a polymerizable compound (B) having at least one structure selected from a biphenyl structure, a bisphenol A structure, a fluorene structure, and a naphthalene structure in the molecule. Material composition characterized.

R1 represents hydrogen or a methyl group, and R2 represents an alkylene group having 1 to 3 carbon atoms.   The material composition according to claim 1, comprising a polymerization initiator (C).   The material composition according to claim 1 or 2, further comprising a polymerizable compound (D) having two or more polymerizable vinyl groups in the molecule. The material composition according to any one of claims 1 to 3, wherein the polymerizable compound (B) is at least one selected from the group of compounds represented by chemical formulas 2, 3, 4, and 5. object.

R3 represents an organic group having a radically polymerizable functional group, and R4 represents hydrogen, an alkyl group, or an organic group having a radically polymerizable functional group.

R5 represents hydrogen or a methyl group, and A represents a direct bond or 1 to 3 methylene groups.

R7 represents an organic group having a radical polymerizable functional group, and R8 represents a hydrogen, an alkyl group or an organic group having a radical polymerizable functional group.

R9 represents an organic group having a radically polymerizable functional group, and R10 represents hydrogen, an alkyl group, or an organic group having a radically polymerizable functional group)   An optical element comprising a cured product of the material composition according to any one of claims 1 to 4.   A composite optical element comprising: an optical base material; and a cured product of the material composition according to any one of claims 1 to 4 laminated on the optical base material.

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