JPH092841A - Composite type optical element - Google Patents

Abstract

PURPOSE: To improve adhesive strength of the interface between a resin and glass without depending on SiO2 content in compounding glass by including at least one or more components of a resin containing a phosphorus compound in an optical resin. CONSTITUTION: This composite type optical element is obtained by including at least one or more components of a resin containing a phosphorus compound into an optical resin layer of a composite optical element obtained by joining and forming the optical resin layer having a desired form onto the surface of a glass substrate. The resin containing the phosphorus compound includes e.g. a resin forming firm bond between the glass side and phosphoric acid group, etc., and forming a chemical bond to the resin side, a resin containing a phosphorus (compound) in the structural formula of the resin, a resin obtained by adding an inorganic phosphorus compound (e.g. phosphoric acid or pyrophosphoric acid) to a resin or a resin obtained by adding an organophophorus compound (e.g. phosphate) to a resin. The resin containing the phosphorus compound is used by adding to the optical resin as the main component or as a layer between the optical resin and glass.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite optical element having a resin layer bonded to the surface of a glass substrate.

[0002]

2. Description of the Related Art In recent years, as lenses used in optical systems such as cameras and video cameras, aspherical lenses have been used for the purpose of reducing the number of lenses and making the optical system compact. The aspherical lens is a general term for lenses whose surface shape is deviated from a spherical surface, and the surface shape is an aspherical surface in order to remove spherical aberration generated in the spherical lens. The aspherical lens includes a plastic aspherical lens (plastic molded lens) and a glass aspherical lens (glass molded lens), and a composite type having a structure in which a thin aspherical resin layer is bonded to the surface of the spherical glass lens. An aspherical lens has been developed and is generally called a replica lens.

In such a compound type aspherical lens, in many cases, stress remains at the interface between the resin and the glass due to curing shrinkage during polymerization of the resin, difference in thermal expansion coefficient between the resin and the glass, and the like. There is. Therefore, if the adhesive strength between the resin and the glass is insufficient, the residual stress is likely to cause peeling at the interface between the resin and the glass.

Conventionally, as a means for increasing the adhesive strength at the interface, a method of subjecting the glass surface to a silane coupling treatment (Japanese Patent Laid-Open No. 54-6006, etc.) has been widely adopted. As the resin, high heat resistance, high elasticity, high hardness,
Urethane acrylate or urethane methacrylate (hereinafter abbreviated as urethane (meth) acrylate) is often used because of its characteristics such as toughness.

[0005]

However, the above-mentioned conventional composite optical element such as a replica lens has the following problems.

First, in the method of subjecting the glass surface to the silane coupling treatment, there is a problem that the effect of the silane coupling treatment can hardly be obtained with a glass having a low SiO ₂ content. As a solution to this problem,
A method has also been proposed in which a SiO ₂ film or the like is deposited on the surface of glass having a low SiO ₂ content, and a silane coupling treatment is performed on the SiO ₂ film (Japanese Patent Application Laid-Open No. 5-221693).
This method has a problem that peeling is likely to occur at the interface between the SiO ₂ film and the base glass.

Further, a technique has been proposed in which a resin portion forming an aspherical surface is separately molded and attached to a glass lens with a photo-curing adhesive (Japanese Patent Laid-Open No. 235025/1992). The curing process is performed twice, resulting in high cost. In addition, since the resin is adhered after the polymerization is completed, there is a problem that the optical resin and the adhesive cannot be copolymerized and sufficient adhesive strength cannot be obtained at the interface between the optical resin and the adhesive. .

Secondly, urethane (meth) acrylate, which has been widely used in the past, does not have sufficient adhesive strength.
The above-mentioned problem of peeling due to residual stress remains. Further, in general, urethane (meth) acrylate is a highly viscous liquid, and in some cases is a solid wax, and therefore, when used in applications such as a replica lens for forming a resin portion by molding, poor moldability is a problem. Become.

More specifically, urethane (meth) acrylate is often used for replica lenses and the like, but polyfunctional urethane (meth) acrylate tends to have distortion after curing. Therefore, a large residual stress is generated at the interface between the resin and the glass, so that if the adhesive force between the glass and the resin is weak, peeling is likely to occur. Further, in the case of polyfunctional urethane (meth) acrylate, unpolymerized functional groups are likely to remain, so that there is a problem that the accuracy of the molding surface is deteriorated due to the progress of polymerization after molding. In this case, it is possible to complete the polymerization of the unpolymerized functional group by heating, but the number of steps is increased and a long heating step is required, resulting in a significant increase in cost.

An example of using urethane (meth) acrylate in a composite optical element is disclosed in Japanese Patent Laid-Open No. 4-1983.
No. 12 publication is known. According to this, a resin containing urethane modified polyester (meth) acrylate, trifunctional urethane (meth) acrylate, and monofunctional urethane (meth) acrylate is used as the optical resin. The reason why urethane modified polyester (meth) acrylate is used is to impart toughness and impact resistance to the resin part, but since the resin contains a polyester structure, the resin has high viscosity and monofunctional urethane (meth) acrylate is used. In addition, it is necessary to dilute it to 10 to 40% to reduce the viscosity. In addition, since the polyester structure is crystalline, it tends to cause clouding and is not suitable as an optical material. Further, although trifunctional urethane (meth) acrylate is added, as described above, the trifunctional urethane (meth) acrylate has a problem that strain is likely to remain after curing and unpolymerized functional groups are likely to remain.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a composite type optical element in which the interface between the glass and the resin layer is not easily peeled off.

[0012]

In order to achieve the above-mentioned object, the inventors of the present invention have conducted extensive studies and as a result, as a result of the presence of a phosphorus-containing compound in the optical resin, the glass composition, particularly SiO ₂ containing The inventors have found that a sufficient adhesion strength can be obtained at the interface between the resin and the glass regardless of the ratio, and as a result, a composite optical element in which the resin layer is difficult to peel off is obtained, and the first invention has been completed.

Further, the relationship between the structure of various urethane (meth) acrylates and the residual strain was examined, and the bifunctional urethane (meth) acrylate had the smallest strain, the low viscosity and the good moldability, and the adhesive force with glass. Therefore, the second invention was completed.

That is, the composite optical element of the first invention is
In a composite optical element formed by bonding and forming an optical resin layer having a desired shape on the surface of a glass substrate, the optical resin layer is made of a resin containing at least one component of a resin containing a phosphorus compound.

The composite optical element of the first invention is the composite optical element as described above, wherein the resin containing the phosphorus compound is an acrylate or a methacrylate containing phosphoric acid or a phosphoric acid ester in the structure. A structure in which the resin containing a compound is an acrylate or a methacrylate represented by the following general formula (1),

[0016]

Embedded image

[Wherein R ₁ is H, a phenyl group, and C _{1 to} C ₁₀
Represents an alkyl group or a cycloalkyl group, and R ₂ is H
Or an CH _3. In addition, m represents an integer of 1 to 5,
n represents 1 or 2. A constitution in which the resin containing the phosphorus compound is prepared by adding an inorganic phosphorus compound or an organic phosphorus compound to the resin, and the resin containing the phosphorus compound is 0.05% by weight or more and 20% by weight or more. In the composite optical element formed by bonding and forming an optical resin layer having a desired shape on the surface of the glass base material containing phosphorus below, a first layer is formed on the glass base material surface by a resin containing a phosphorus compound, A structure in which the optical resin layer has a multi-layer structure by superposing and polymerizing an optical resin on the first layer, or a composite type optical structure in which an optical resin layer having a desired shape is formed by bonding on the surface of a glass substrate. In the element, the optical resin layer is formed by adding and mixing a resin containing a phosphorus compound to the optical resin.

The composite optical element of the second invention is a photocurable optical resin containing an aliphatic hydrocarbon having a branched main chain skeleton and containing urethane acrylate or urethane methacrylate having two functional groups at the ends. The composition is formed by curing the composition in a desired shape on the surface of the glass substrate.

The composite optical element of the second invention is the composite optical element as described above, wherein the photocurable resin composition for optics has 3 to 2 carbon atoms in the aliphatic hydrocarbon between the terminal functional groups.
A composition containing a urethane acrylate or urethane methacrylate of 0, and the photocurable optical resin composition is a bifunctional urethane acrylate or a bifunctional urethane methacrylate obtained by reacting two molecules of diisocyanate with an alcohol having one hydroxyl group. Or a composition containing the bifunctional urethane acrylate or bifunctional urethane methacrylate obtained by reacting two molecules of monoisocyanate with a diol having two hydroxyl groups at the terminal. is there.

[0020]

In the first invention, the presence of a phosphorus-containing compound in the optical resin forms a strong bond by the phosphate group on the glass side, while the resin side copolymerizes with the phosphorus compound to form a chemical bond. Since it is formed, sufficient adhesive strength can be obtained at the interface between the resin and the glass regardless of the glass composition. Therefore, it is possible to obtain a composite optical element in which the resin layer does not easily peel off.

In the second invention, a bifunctional urethane (meth) acrylate, which is an aliphatic hydrocarbon having a branched main chain skeleton, is used as an optical resin, and this resin has an advantage of good moldability and at the same time, a resin. The strain (residual stress) in the layer is small, and the adhesive force with glass is high. Therefore, it is possible to obtain a composite optical element in which the resin layer does not easily peel off.

Hereinafter, the present invention will be described in detail.

First, the first invention will be described.

The first invention is characterized in that the optical resin layer in the composite optical element is made of a resin containing at least one resin containing a phosphorus compound.

Here, the resin containing a phosphorus compound may be a resin that forms a strong bond with the glass side by a phosphoric acid group or the like, while forming a chemical bond with the resin side. In addition to those containing (compound), inorganic phosphorus compounds (phosphoric acid, pyrophosphoric acid, phosphorus pentoxide, triphosphoric acid,
(Metaphosphoric acid, peroxophosphoric acid, phosphorus amide, phosphorus imide, etc.) may be added, and an organic phosphorus compound (phosphoric acid ester, phosphorus ylene compound, etc.) in the resin may be added.
May be added.

As the resin containing a phosphorus compound in its structure,
Specific examples include compounds represented by the following general formula (1).

[0027]

Embedded image

[Wherein R ₁ is H, a phenyl group, C ₁ -C ₁₀
Represents an alkyl group or a cycloalkyl group, and R ₂ is H
Or an CH _3. In addition, m represents an integer of 1 to 5,
n represents 1 or 2. This compound is a compound (monomer) having a phosphoric acid ester, and is copolymerized with the optical resin at the double bond portion of the acrylic acid group.

The resin containing the phosphorus compound may be a resin composed of a single component, or may be a resin composed of a plurality of resins having different structures containing the phosphorus compound. The resin containing a phosphorus compound may be diluted with a photocurable monomer such as methyl acrylate or ethyl acrylate.

The resin containing the above phosphorus compound is used by adding it to the main optical resin, or when the optical resin layer has a multi-layer structure as described later, the resin between the optical resin and the glass is used. Used as a layer.

Here, examples of the main optical resin include urethane (meth) acrylate (based resin) and epoxy (meth) acrylate (based resin).

The urethane (meth) acrylate may be any of monomers (monofunctional monomers, polyfunctional monomers), oligomers (prepolymers), polymers (polyurethane (meth) acrylates, etc.).

As the urethane (meth) acrylate,
Specific examples include compounds represented by the following general formula (2).

[0034]

Embedded image

[Wherein R ₁ represents H or CH ₃ , and R ₂
Represents a phenyl group, a C ₄ -C ₂₀ alkyl group, a cycloalkyl group or an aryl group. ]

Examples of urethane (meth) acrylates include various commercially available urethanes (meth) such as UA-101H (manufactured by Kyoeisha Chemical Co., Ltd.) and U-4HA (manufactured by Shin Nakamura Chemical Co., Ltd.). ) Acrylate resin (commercially available as UV curable resin, optical adhesive, resin modifier, etc.)
It is also possible to use it by selecting from.

The optical resins as the main component may be used alone or in a mixture of two or more.

In the present invention, the adhesive force with the glass is generated by the formation of a bond to the glass by the phosphoric acid group, and therefore the resin containing the phosphorus compound need not occupy the whole of the main optical resin. It suffices if the adhesive surface between the optical resin and the glass is covered. Therefore, after coating the glass surface with a resin containing a phosphorus compound, an optical resin may be laminated on the glass surface to form an optical resin layer having a multilayer structure.

In order to obtain high adhesive strength, it is necessary to contain phosphorus in the optical resin in an amount of 0.05% by weight or more, but when coating the glass surface, 0.05% by weight or more of phosphorus is included in the coating layer. Is sufficient, and the ratio of phosphorus to the entire optical resin layer does not matter.

In order to prevent an increase in the water absorption rate of the optical resin, it is necessary that the phosphorus contained in the optical resin be 20% by weight or less.

The polymerization initiator is added to the resin as needed. Polymerization with a polymerization initiator can be initiated by light polymerization, thermal polymerization, radiation polymerization or the like. As the photopolymerization initiator, benzophenone, benzoin ethyl ether, benzyl methyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-chlorothioxazoline, p
As the thermal polymerization initiator such as ethyl dimethylaminobenzoate, cumene hydroxyperoxide, benzoyl peroxide, azobisisobritonitrile, azobisdimethylvaleronitrile and the like can be used.

Examples of other additive components in the optical resin layer include a releasing agent and a diluting resin component.

In the composite optical element of the present invention, an optical resin containing the above-mentioned resin containing a phosphorus compound is bonded and molded in a desired shape on the surface of a glass substrate to form an optical resin layer. Here, a mold or the like may be used to form the optical resin layer into a desired shape.

The glass substrate in the composite optical element is not particularly limited as long as it is a glass that satisfies the required optical characteristics. Further, the shape of the glass substrate is not particularly limited, and those having a shape suitable for various optical elements such as a plate shape, a lens shape and a prism shape are used.

In the first invention, a simple method such as blending or coating can be used, and it is not necessary to carry out prepolymerization even in the case of coating.
As a process, the molding of the optical resin, the copolymerization of the optical resin and the coating layer, and the adhesion of the coating layer and the glass can all be achieved with a single irradiation of light. Therefore, as compared with the technique of separately molding the resin portion forming the aspherical surface and adhering it to the glass lens with a photo-curing adhesive (Japanese Patent Laid-Open No. 235025/1992), the cost is shorter and the cost is lower. Also,
Compared with the method of performing silane coupling treatment, since the drying step and the heat treatment step are unnecessary, the present invention is shorter in time and lower in cost, and further, in the present invention, high adhesion is achieved regardless of the glass type of glass. Strength can be obtained.

Next, the second invention will be described.

The second invention is a photocurable resin containing urethane acrylate or urethane methacrylate, which is an aliphatic hydrocarbon having a branched main chain skeleton and has two functional groups at the terminals, as an optical resin in a composite optical element. A mold optical resin composition is used.

Here, the bifunctional urethane (meth) acrylate has the smallest distortion, the low viscosity, and the high adhesive strength with glass, as compared with other polyfunctional urethane (meth) acrylates. The reason why the strain (stress) is small is related to the special polymerization-curing shrinkage property of the resin having the structure of the present invention. When the resin having the structure of the present invention is polymerized, the polymerization shrinkage occurs in advance of the increase in the elastic modulus as compared with the other resins. In addition, it was clarified as a result of application analysis by the finite element method that the resin having such a polymerization property has a small distortion due to the polymerization.

The bifunctional urethane (meth) acrylate used in the present invention is characterized in that unpolymerized functional groups do not remain. Therefore, the polymerization of unpolymerized functional groups proceeds after molding, so that the precision of the molding surface is improved. The problem of getting worse does not occur.

When the main chain of the urethane (meth) acrylate is a branched aliphatic hydrocarbon, the resin has a low viscosity, so that the moldability is improved. Ordinary urethane (meth) acrylate is often a highly viscous fluid or a waxy solid, but the resin used in the present invention has a low viscosity, that is, good moldability. This means that the resin part is produced by molding a monomer. It is very preferable in manufacturing a composite optical element such as a replica lens.

Compared with other resins, the resin of the structure of the present invention
Experiments have shown that the adhesive strength with glass is high. Further, regarding the toughness and impact resistance, the resin having the structure of the present invention containing no polyester structure can provide sufficient characteristics.

As the method for synthesizing the bifunctional urethane (meth) acrylate used in the present invention, for example, two molecules of alcohol having one hydroxyl group are added to diisocyanate which is an aliphatic hydrocarbon having a branched main chain, or , A diol having a branched main chain and having two hydroxyl groups at both ends, and a monoisocyanate
Synthesized by adding molecules.

In addition, as the bifunctional urethane (meth) acrylate used in the present invention, a commercially available bifunctional urethane (meth) acrylate (which is an aliphatic hydrocarbon having a branched main chain) may be used. . In this case, in order to cure and mold the resin portion by photopolymerization, 1-hydroxycyclohexyl phenyl ketone (Tokyo Chemical Industry Co., Ltd.)
An appropriate amount of a photopolymerization initiator (such as a product manufactured by Co.) is added and used.
When using a commercially available bifunctional urethane (meth) acrylate-based optical adhesive to which a photopolymerization initiator has already been added, it is not necessary to further add the photopolymerization initiator.

The carbon number of the main chain aliphatic hydrocarbon in the bifunctional urethane (meth) acrylate used in the present invention is preferably 3 to 20, which is the viscosity of the resin and the shrinkage due to polymerization and curing of the resin. This is to adjust the characteristics, such as distortion after polymerization.

In the present invention, in order to enhance the adhesive strength,
If necessary, the surface of the glass substrate can be subjected to silane coupling treatment.

The field of application of the present invention (first and second inventions) is not limited to the replica lens, and any composite type optical element (including composite type optical component) manufactured by bonding resin and glass together is manufactured. The joining technique of the present invention can be used for

Specifically, for example, a camera lens, a video lens, a photographic lens, a light source lens for optical communication, a large-diameter lens, a spectacle lens, a pickup lens of a compact disc player, a lens of a projection television, a phase grating low-pass lens. It can be used for composite optical elements such as filters, color filters, phase grating filters, anamorphic lenses, lenticular lenses, gratings, prisms, zone plates, Fresnel lenses and holographic lenses.

[0058]

Embodiments of the present invention will be described below.

First, an embodiment relating to the first invention will be described.

Examples 1 to 4 As the optical resin, tetrafunctional urethane methacrylate (hereinafter referred to as resin A) produced by adding alcohol represented by the following structural formula (3) to hexamethylene diisocyanate was used.

[0061]

Embedded image

As the glass, white plate (HOYA
Co., Ltd .: SiO ₂ content 75 mol%), BaCD5
(Also 55 mol%), TaF1 (also 5 mol%),
FCD1 (also 0 mol%; fluorophosphate glass) 30
A plate-shaped product of × 20 × 5 mm was used.

The above-mentioned glass test piece polished on both sides was thoroughly washed, and a phosphorus-containing compound (MR-100: Kyoeisha Chemical Co., Ltd.) to which a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone: manufactured by Tokyo Chemical Industry Co., Ltd.) was added. (Manufactured by Co., Ltd.)
(Containing 14.76% by weight in terms of phosphorus) was spin coated (3600 rpm × 5) on each of the two glass surfaces.
Seconds).

Resin A to which a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone: manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added was coated between two glass coating surfaces with an area of 5 × 20 mm and a thickness of 0. Insert to be 6mm,
Ultraviolet rays (high pressure mercury lamp: illuminance under white glass sample 21.
9 mW / cm ² ) for 5 minutes to photo-cure the resin portion to obtain a sample for measuring adhesive strength.

Examples 5 to 5 A resin containing a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) added thereto without spin-coating a phosphorus-containing compound was used. -100: Same as Examples 1 to 4 except that a resin (containing 0.74% by weight in terms of phosphorus) added with Kyoeisha Chemical Co., Ltd. was sandwiched between glasses and photocured to form a sample. Then, a sample was obtained.

Examples 9 to 12 Examples were carried out except that a phosphorus-containing urethane acrylate-based photocurable adhesive (OP-3010P: manufactured by Denki Kagaku Kogyo) was used as the phosphorus-containing compound and was spin-coated. Samples were obtained in the same manner as in Examples 1 to 4.

A plasma emission spectral analyzer (SPS
1200 VR: Seiko Denshi Kogyo Co., Ltd.) analyzed the components of the photocurable adhesive (OP-3010P), and as a result, it contained 0.08% by weight of phosphorus.

Examples 13 to 16 As phosphorus-containing compounds, phosphorus-containing compounds (MR-10
0: manufactured by Kyoeisha Chemical Co., Ltd. (14.7 in terms of phosphorus)
6% by weight) was diluted with a photocurable monomer (methyl acrylate), and a resin having a phosphorus content of 0.05% by weight was used for spin coating.
Samples were obtained in the same manner as ~ 4.

Comparative Examples 1 to 4 As a phosphorus-containing compound, a phosphorus-containing compound (MR-10
Samples were obtained in the same manner as in Examples 13 to 16 except that (0) was diluted with a photocurable monomer, and a resin having a phosphorus content of 0.03% by weight was used for spin coating.

Comparative Examples 5 to 8 A sample was prepared by photocuring resin A sandwiched with a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) between untreated glasses without spin coating with a phosphorus-containing compound. Samples were obtained in the same manner as in Examples 1 to 4 except for the above.

Comparative Examples 9 to 12 The surface of each glass was coated with a silane coupling agent (silane coupler KBM50 without spin-coating the phosphorus-containing compound).
3: manufactured by Shin-Etsu Chemical Co., Ltd.), and then subjected to silane coupling treatment, and then sandwiched with resin A between the glass surfaces subjected to silane coupling treatment and photocured to prepare samples, and the same procedure as in Examples 1 to 4 To obtain a sample.

Measurement of Shear Strength The samples obtained in Examples 1 to 16 and Comparative Examples 1 to 12 were mounted on the apparatus shown in FIG. 1, and a shearing force 3 was applied to the adhesive interface 2 via the glass plate 1. The load when the adhesive portion peeled off was measured. Each sample was measured at 3 to 9 points, and the shear strength was calculated from the average value. Table 1 shows the results.

[0073]

[Table 1]

As is clear from Table 1, according to the present invention (Examples 1 to 16), high adhesive strength can be obtained at the interface between the resin and the glass, regardless of the glass type (SiO ₂ content). Recognize.

Next, examples of the second invention will be described.

Examples 17 to 20 As the optical resin, an aliphatic hydrocarbon (C having a branched main chain) was used.
₉ : 2,2,4-trimethyl-hexamethylene group), a difunctional isocyanate synthesized by adding 2 molecules of 2-hydroxyethyl methacrylate to diisocyanate, and a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone). ) Was added to the resin composition.

As the glass, white plate (HOYA
Co., Ltd.), BaCD5 (HOYA Co., Ltd.), T
aF1 (manufactured by HOYA Corporation), FCD1 (HOYA)
(Manufactured by Co., Ltd.) fluorinated glass) 30 × 20 × 5 mm
The plate-shaped product was used.

The above-mentioned glass test pieces polished on both sides were thoroughly washed, and the surface of each glass was treated with 1 of a silane coupling agent (silane coupler KBM503: manufactured by Shin-Etsu Chemical Co., Ltd.).
It was immersed in a wt% ethanol solution, dried at 80 ° C. for 20 minutes, and subjected to silane coupling treatment. Two glasses were faced to each other through a spacer so that the spacing was 0.6 mm with the glass surface subjected to silane coupling treatment inside, and the resin composition prepared above had an area of 5
Insert it so that it will be × 20 mm, and use ultraviolet rays (high pressure mercury lamp:
An illuminance of 21.9 mW / cm ² ) under a white plate glass sample was set to 5
The resin composition was photocured by irradiation for a minute to prepare a sample for measuring the adhesive strength.

Examples 21 to 24 An optical resin is an aliphatic hydrocarbon (C ₁₆ : name 3,6,7,10-tetramethyl-dodecane group) having a branched main chain having two hydroxyl groups at both ends. Same as Examples 17 to 20 except that a resin composition obtained by adding a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) to a bifunctional urethane methacrylate synthesized by adding two molecules of methacryloyl isocyanate to a diol was used. Then, a sample was obtained.

Comparative Examples 13 to 16 Hexamethylene diisocyanate was used as an optical resin,
Examples 17 to 17 except that a resin composition obtained by adding a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) to a tetrafunctional urethane methacrylate synthesized by adding 2 molecules of hydroxypropyl dimethacrylate was used.
A sample was obtained in the same manner as 20.

Comparative Examples 17 to 20 As an optical resin, AT-600 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd .: a structure in which two molecules of phenylglycidyl ether acrylate are added to tolylene diisocyanate)
Samples were obtained in the same manner as in Examples 17 to 20 except that a resin composition containing a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) was used.

Measurement of Shear Strength The samples obtained in Examples 17 to 24 and Comparative Examples 13 to 20 were mounted on the apparatus shown in FIG. 1, and a shearing force W was applied to the adhesive interface 2 via the glass plate 1. The load when the adhesive portion peeled off was measured. In addition, each of a plurality of samples (3 to 9
(Point) was measured, and the shear strength was calculated from the average value. The results are shown in Table 2. The viscosity of the resin used is also shown.

[0083]

[Table 2]

As is clear from Table 2, according to the present invention (Examples 17 to 24), high adhesive strength can be obtained at the interface between the resin and the glass. In Examples where glass breakage occurs preferentially, the strength of the glass itself is weaker than the adhesive strength at the interface, indicating that the adhesive strength is even higher than the measured value.

Examples 25 to 32 and Comparative Examples 21 to 28 Using the same resins as those used in Examples 17 to 24 and Comparative Examples 13 to 20, silane coupling treatment was performed in the same manner, and the flat glass plate surface was rounded. Each resin is 30mmφ ×
Samples were obtained in the same manner as in Examples 17 to 24 and Comparative Examples 13 to 20 except that a replica lens was manufactured by joining and forming to a thickness of 300 μm.

As a result, the resins used in the present invention (Examples 25 to 32) had a lower viscosity and better moldability than the comparative examples. In addition, the strain in the resin of the replica lens of the obtained sample was measured by a precision strain gauge, and further ± 40
The temperature cycle of ° C was applied 20 times, and the presence or absence of peeling at the interface between glass and resin was examined. Table 3 shows the results.

[0087]

[Table 3]

As is clear from Table 3, according to the present invention (Examples 25 to 32), it is apparent that a replica lens having an apparently small amount of strain and in which peeling does not occur even after being subjected to a temperature cycle is obtained. .

Although the present invention has been described above with reference to the preferred embodiments, the present invention is not necessarily limited to the above embodiments.

For example, in Examples 25 to 32, a titanate coupling agent or an aluminum coupling agent can be used instead of the silane coupling treatment.

Further, in Examples 25 to 32, the composite optical element can be manufactured without performing the silane coupling treatment.

Furthermore, the first invention and the second invention can be combined and implemented.

[0093]

As described above, in the composite optical element of the first invention, the presence of the compound containing phosphorus in the optical resin makes it possible to obtain a sufficient adhesive strength at the interface between the resin and the glass regardless of the glass composition. Is obtained. Therefore, the resin layer is difficult to peel off.

Further, the composite optical element of the second invention uses a bifunctional urethane (meth) acrylate as an optical resin, and this resin has an advantage of good moldability and has a strain (residual residue) in the resin layer. Low stress) and high adhesion to glass. Therefore, it is possible to obtain a composite optical element in which the resin layer does not easily peel off.

[Brief description of drawings]

1 is a side view showing an apparatus for measuring shear (peel) strength.

[Explanation of symbols]

 1 Glass plate 2 Bonding interface 3 Shearing force

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masahiro Yoshida 2-7-5 Nakaochiai, Shinjuku-ku, Tokyo Hoya Co., Ltd.

Claims (11)

[Claims] 1. A composite optical element comprising a glass substrate and an optical resin layer having a desired shape bonded to the surface of the glass substrate, wherein the optical resin layer comprises a resin containing at least one component of a resin containing a phosphorus compound. A composite optical element characterized by the above. 2. The composite optical element according to claim 1, wherein the resin containing a phosphorus compound is an acrylate or a methacrylate containing phosphoric acid or a phosphoric acid ester in its structure. 3. The composite optical element according to claim 2, wherein the resin containing a phosphorus compound is an acrylate or a methacrylate represented by the following general formula (1). Embedded image [In the formula, R ₁ represents H, a phenyl group, a C ₁ -C ₁₀ alkyl group or a cycloalkyl group, and R ₂ represents H or CH ₃ . Further, m represents an integer of 1 to 5, and n is 1 or 2
Is shown. ] 4. The composite optical element according to claim 1, wherein the resin containing the phosphorus compound is prepared by adding and mixing an inorganic phosphorus compound or an organic phosphorus compound into the resin. 5. The resin containing a phosphorus compound is 0.05
The composite optical element according to claim 1, which contains phosphorus in an amount of 20% by weight or more and 20% by weight or less. 6. A composite optical element comprising an optical resin layer having a desired shape bonded and formed on the surface of a glass substrate, wherein a first layer is formed on the surface of the glass substrate with a resin containing a phosphorus compound. The composite optical element according to any one of claims 1 to 5, wherein the optical resin layer has a multilayer structure by superposing an optical resin on one layer and polymerizing the optical resin. 7. A composite optical element comprising an optical resin layer having a desired shape bonded and formed on the surface of a glass substrate, wherein the optical resin layer is formed by adding and mixing a resin containing a phosphorus compound to the optical resin. The method according to claim 1, wherein
5. The composite optical element according to any one of 5 above. 8. A photocurable optical resin composition comprising a urethane acrylate or urethane methacrylate having a branched main chain skeleton and having two functional groups at the terminal, and a glass substrate surface. A composite optical element characterized by being cured in the desired shape above. 9. The photocurable resin composition for optics contains urethane acrylate or urethane methacrylate in which an aliphatic hydrocarbon between terminal functional groups has 3 to 20 carbon atoms. Composite optical element. 10. A bifunctional urethane acrylate or a bifunctional urethane acrylate obtained by reacting two molecules of diisocyanate with an alcohol having one hydroxyl group in a photocurable optical resin composition.
10. The composite optical element according to claim 8, which contains a functional urethane methacrylate. 11. A photocurable resin composition for optics, comprising a diol having two hydroxyl groups at the end and a monoisocyanate of 2 units.
10. The composite optical element according to claim 8, which contains a bifunctional urethane acrylate or a bifunctional urethane methacrylate obtained by molecular reaction.