JP2003026805A - Shape memory and optical material, optical part and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a shape memory and optical material which is transparent, can be arbitrarily deformed by heating and has shape memory properties, and to provide an optical part and a method for producing the optical part. SOLUTION: This shape memory and optical material is obtained by curing a curable resin composition containing a compound with two or more groups represented by formula (1) (X is CH2 , CH3 CH, (CH3 )2 C, O or S; R<1> is a hydrogen atom, an alkyl group, a carboxy group or its derivative; R<2> is a hydrogen atom, a cyano group, an alkyl group, a substituted alkyl group, a carboxy group or its derivative; n is an integer of 0-5; α is a binding site) and a compound with two or more thiol groups.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a light-transmitting property,
In addition, a novel shape memory property is formed by a curable resin composition that can be arbitrarily deformed by heating, can retain a deformed state by cooling while deformed, and can return to a shape before deformation by reheating. The present invention relates to an optical material, an optical component, and a method for manufacturing an optical component.

[0002]

2. Description of the Related Art Plastic materials used for electronic parts and optical parts are also used for parts where inorganic materials such as glass and quartz have been used in the past due to their features such as easy moldability and light weight. ing. Typical of these plastics are polycarbonate and polymethylmethacrylate. Further, curable resins such as polyfunctional acrylates have also been used for lens materials and the like. Conventionally, injection molding, casting, extrusion molding, spinning, cutting and polishing, bonding, and the like are known as molding methods for such optical resins.

However, although thermoplastic resin materials such as polycarbonate and polymethylmethacrylate have the property that they can be softened and deformed by heating, the fluidity of the resin also increases in the heated state. Therefore, although it is suitable for injection molding using a mold, etc., when changing the shape in a place where there is no molding machine, if you try to heat and deform it, the resin will flow and the shape will change. There is a problem that it cannot be controlled precisely. Moreover, they have an irreversible property that once they fail to deform, they do not recover even if they are heated. Further, the curable resin has been conventionally molded by a method such as casting of a lens or the like, cutting and polishing, etc., but it has never been used after being cured and then deformed by heating.

Further, the cured resin of polyfunctional (meth) acrylate has the property of transmitting light in the visible light region and having good visual transparency, and is therefore used in various optical parts. However, in recent years, in the field of such optical components, not only downsizing and weight reduction of components, but also high speed and high density of information recording, reading and communication are required, and therefore, they are used in order to meet these requirements. The wavelength of light is short, that is, it is spreading from blue to the ultraviolet region.

However, in the case of a polyfunctional (meth) acrylate resin cured product which has been conventionally used, since the absorption of light is large around the ultraviolet region where the wavelength of light is short, there is a problem in transparency, and a short wavelength is used. It is difficult to deal with light. Further, there is also a problem that the light transmittance in the short wavelength region is reduced due to the residue of the radical generator added at the time of curing. Moreover, since light in the short wavelength region has high energy, when a resin with low transparency in the short wavelength region is used for transmitting blue or near-ultraviolet light, the resin cured product deteriorates due to the light that cannot be transmitted through the resin and is absorbed. There is also a problem that the life of the resin cured product is shortened due to this. In addition to this, the cured resin of a polyfunctional (meth) acrylate has a drawback that it has a high water absorption rate, so that it also has a problem that transparency is impaired by moisture absorption.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has optical transparency, can be arbitrarily deformed by heating, and is cooled while being deformed. The shape-memory optical material, the optical component, and the optical component, in which the shape after deformation is retained by the above-mentioned method, and the shape can be easily returned to the original shape without applying force by reheating as needed It is intended to provide a manufacturing method.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a curable resin capable of giving a glass-like transparent resin cured product at room temperature is cured by an initial curing process. By giving a shape, a step of deforming by applying an external force by holding it at a temperature higher than the glass transition temperature, a step of removing the external force after cooling while keeping it deformed, and maintaining a deformed state different from the initial shape It was found that a transparent optical material having an arbitrary shape can be easily obtained without using a large-scale molding machine or the like. In addition, it was found that a composition comprising a compound having a predetermined norbornene structure and a compound having two or more thiol groups has excellent transparency and water resistance and is easily deformed by heating, and thus the present invention is completed. I arrived.

The shape-memory optical material of the present invention comprises a compound (A) having two or more groups represented by the above formula (1),
It is characterized by being obtained by curing a curable resin composition containing a compound (B) having two or more thiol groups. Further, the method for producing an optical component of the present invention is a curing step of imparting an initial shape by curing a curable resin composition capable of giving a glass-like transparent resin cured product at room temperature, a glass of the resin cured product. It is characterized in that it undergoes a deformation step of holding at a temperature equal to or higher than the transition temperature and deforming by applying an external force, a deformation holding step of cooling while still deformed, removing the external force, and holding a deformed state different from the initial shape. To do. Furthermore, the optical component of the present invention is characterized by being manufactured using the method for manufacturing an optical material of the present invention.

[0009]

EFFECTS OF THE INVENTION The shape-memory optical material of the present invention has the above-mentioned constitution and, in addition to the shape-memory property, has a property of transmitting light in a wide range from the visible light region to the near-ultraviolet region. Since the norbornene skeleton has high hydrophobicity, it has high water resistance and can be suitably used for optical parts and the like. Further, the method for producing an optical component of the present invention is a novel production method capable of forming an optical component by utilizing the shape memory property of a transparent curable resin, and produces an optical component having a complicated shape. When assembling, it does not require skilled work such as cutting or joining transparent parts that allow light to pass, and there is little loss of light when passing light to the completed parts, and because of excellent reproducibility, Extremely useful. Further, the optical component of the present invention has excellent transparency and high water resistance, and can be suitably used for light emitting diodes, various lenses, and the like, and particularly has a transmittance of light having a short wavelength in the blue to near-ultraviolet region. Since it is high, it can be suitably used as a coating material for an information recording medium, a pickup lens, and its peripheral material.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. <Compound (A)> In the shape-memory optical material of the present invention, the compound (A) having two or more groups represented by the formula (1) may be only one type, or two or more types may be used in combination. You can Then, in the above formula (1), X is CH
₂ , (CH ₃ ) ₂ C, CH ₃ CH, O or S, among which CH ₂ , (C
It is preferable to use a compound having a skeleton of H ₃ ) ₂ C or CH ₃ CH, because a resin cured product having excellent water resistance can be obtained. In the above formula (1), when X is 2 or more (that is, when n = 1 to 5), the Xs are usually the same type, but may be different types. In addition,
Norbornene represented by the formula (1) (X = CH ₂ , n = 0
in the case of. ) Or a skeleton similar thereto (X = (CH ₃ ) ₂ C,
CH ₃ CH, O or S, when n = 1 to 5. ) Is collectively referred to as "a skeleton such as norbornene".

In the above formula (1), R ¹ is a hydrogen atom, an alkyl group (methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group). Etc.) or a carboxyl group or a derivative thereof (ester, acid anhydride, amide, etc.). Among these, a hydrogen atom or a methyl group is preferable because it can be a resin cured product having excellent water resistance, and when a hydrogen atom is further used, a compound represented by the above formula (1) can be obtained by using a Diels-Alder reaction. In the case of synthesizing, less heating is required, and it is possible to synthesize easily, which is more preferable.

In the above formula (1), R ² is a hydrogen atom, an alkyl group (methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group). Group), a substituted alkyl group, a cyano group or a carboxyl group or a derivative thereof (ester, acid anhydride, amide, etc.), specifically, -H,
_{-CH 3, -CH 2 OH, -CN} , -CH 2 COOR '
(R 'is an alkyl group such as a methyl group and an ethyl group, an aryl group and the like) and COOR' (R 'is an alkyl group such as a methyl group and an ethyl group, an aryl group and the like) and the like. Among these, a hydrogen atom or an alkyl group is preferable from the viewpoint of excellent water resistance.

Further, in the above formula (1), R ¹ and R
^When at least one of ² is a carboxyl group, it can be dissolved in an alkaline aqueous solution, and therefore, when this composition is used as a solution and used for applications such as coating, water can be used as a solvent, and a metal can be used. The adhesiveness with can be improved. Therefore, it is preferable that at least one of R ¹ and R ² is a carboxyl group. Moreover, when using 2 or more types of said compound (A), it is more preferable to make some or all the said carboxyl group containing compound.

In the above formula (1), n is 0 to
5, preferably 0 to 2, particularly preferably 0 or 1 is shown. When n exceeds 5, the viscosity of the compound (A) becomes too high and it becomes difficult to handle, which is not preferable.
On the other hand, when n is 2 or less, the viscosity of the compound (A) can be in an appropriate range, which is preferable. Also, n
Is preferably 1, because the heat resistance of the cured resin product can be increased, and n is preferably because the composition can be easily synthesized and the adhesiveness can be improved. In the chemical formula (1), α represents a binding site. The structure bound at the α binding site is not particularly limited, and may form a ring structure with R ¹ .

Specific examples of the above-mentioned "compound (A)" include
Is, for example, a compound represented by the above formula (2) or (3)
Can be However, in the formula (2), X is
CH _Two, CH_ThreeCH, (CH_Three)_TwoC, O or S
M¹, M^Two, M^ThreeAre each independently an integer from 0 to 5
Represents R⁸, R⁹Are each independently a hydrogen atom or
Represents a chill group. In the formula (3), Z is the above formula.
It is a group represented by (4), and Y is an alkyl group having 1 to 5 carbon atoms.
It is a ru basis. And, a is an integer of 1 to 4, b is 0 to 2
Is an integer, a ′ and b ′ are integers from 0 to 3, and m is
It is 0 or 1. Furthermore, when a + b = 4-m and m = 1
Is a '+ b' = 3, and a + a '> 1.
Further, in the formula (4), R⁷Is an alkylene group having 1 to 4 carbon atoms
Or represents a polyalkylene glycol residue, R¹⁰
Represents a hydrogen atom or a methyl group. X is the above formula
It is synonymous with (1). It should be noted that there are two or more in one molecule
Even if the structures of the groups represented by formula (4) are the same,
It may be different.

More specifically, examples of the compound represented by the above formula (3) include compounds represented by the following formulas (5) to (8). In formulas (5) to (8), R ^{3 to} R
⁶ is a group represented by the formula (4) or a hydroxyalkyl group having 1 to 4 carbon atoms, and the number of groups represented by the formula (4) is at least two.

[Chemical 5]

The method for producing the above-mentioned "compound (A)" is not particularly limited. For example, when X is CH ₂ , a compound having an unsaturated double bond and a carbonyl group is reacted with cyclopentadiene. Can be obtained by the method. n represents an integer of 0 to 5, and the one in which n is 1 or more can be obtained by adding cyclopentadiene or a cyclic diene compound similar to cyclopentadiene in excess to the unsaturated double bond as a raw material. Yes, n = 0
Even when synthesizing the compound (1) for the purpose, some of the compounds not having n = 0 may be produced depending on conditions such as temperature. In particular, when the compound having an unsaturated double bond and a carbonyl group is a compound having an acryloyl group and / or a methacryloyl group (hereinafter, referred to as “(meth) acryloyl group”), cyclopentadiene and Diels Alder can be easily obtained. A reaction occurs and is preferred. In addition, since many types of bifunctional or higher (meth) acrylates are commercially available, there is an advantage that compounds having various skeletons can be selected depending on the availability of raw materials and the intended use. Most preferred as a means for synthesizing the compound (A) ". Cyclopentadiene can be easily obtained by thermally decomposing dicyclopentadiene. Of the above-mentioned “compound (A)”, the compound of X═O or S can be obtained by using furan or thiophene in place of cyclopentadiene.

In the case of synthesizing the above-mentioned "compound (A)" by the Diels-Alder reaction, the compound having an unsaturated double bond as one raw material is, for example, (meth)
Examples thereof include an ester or amide of acrylic acid, itaconic acid, crotonic acid, maleic acid, or a compound having an imide when it is a divalent acid. Among these, a (meth) acryloyl compound derived from (meth) acrylic acid is preferable because it is easily available and the Diels-Alder reaction is easy.

The compounds having a (meth) acryloyl group (in the present specification, acrylate and methacrylate are collectively referred to as "(meth) acrylate") are bisphenol A di (meth) acrylate and bisphenol F diester. (Meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate (for example, manufactured by Toagosei Co., Ltd., trade name “Aronix M21
0 "), ethylene oxide modified bisphenol F di (meth) acrylate (for example, manufactured by Toagosei Co., Ltd., trade name" Aronix M208 "), propylene oxide modified bisphenol A di (meth) acrylate (for example, manufactured by Kyoeisha Chemical Co., Ltd., trade name "Light acrylate BP-4PA"), dimethylol tricyclodecane di (meth) acrylate (for example, manufactured by Kyoeisha Chemical Co., Ltd.,
Trade name "Light acrylate DCP-A"), hexanediol di (meth) acrylate (for example, manufactured by Kyoeisha Chemical Co., Ltd., trade name "Light acrylate 1.6HX-"
A ”), epoxy resin such as bisphenol A diglycidyl ether, and epoxy (meth) acrylate produced by reacting (meth) acrylic acid, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly Tetramethylene oxide di (meth) acrylate, polyester di (meth) acrylate, neopentyl glycol di (meth)
Bifunctional (meth) acrylates such as acrylates; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acrylate of trihydroxyethyl isocyanurate (for example, manufactured by Toagosei Co., Ltd., trade name “Aronix M
315 ") and other trifunctional (meth) acrylates; pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, cresol novolac polyglycidyl ether and (meth) acrylic acid-produced epoxy (meth) ) Polyfunctional (meth) acrylates such as acrylate, polyfunctional acrylamides such as ethylenebisacrylamide, hexamethylenebis (meth) acrylamide, polyfunctional cyanoacrylates such as tripropylene glycol biscyanoacrylate and 1,6-hexanediol biscyanoacrylate Etc. You may use these 2 or more types together.

Further, the preferable type of the compound having an unsaturated double bond used when synthesizing the "compound (A)" by the Diels-Alder reaction varies depending on the purpose of the curable resin composition to be obtained. For example, when a resin cured product is desired to have high mechanical strength, high elastic modulus and high glass transition temperature, a (meth) acrylate having a residue of a ring structure such as bisphenols, dicyclopentadiene, isocyanuric acid, or pentaerythritol tris- Polyfunctional (meth) acrylates such as (meth) acrylate are preferred. When a flexible resin cured product is required or when it is used as an additive for lowering the elastic modulus of the cured product, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate,
A compound having a flexible structure such as polyester di (meth) acrylate and polyurethane (meth) acrylate can be preferably used.

When the compound having an unsaturated double bond used when synthesizing the above-mentioned "compound (A)" is composed of an aliphatic skeleton, the curing reactivity is particularly excellent and the radical generator is used. It can be cured at a relatively low temperature without addition. Furthermore, since a cured product having a high Abbe number, which is important as an optical property, can be obtained, it can be used particularly preferably.

The second method for easily synthesizing the above-mentioned "compound (A)" is a reaction between an acid anhydride having a skeleton such as norbornene and a polyhydric alcohol. Examples of the acid anhydride include nadic acid anhydride and methyl nadic acid anhydride. Since such an acid anhydride and an alcohol easily react with each other without a catalyst or with a basic compound as a catalyst, the above-mentioned "compound (A)" having two or more skeletons such as norbornene can be obtained. In addition to the above-mentioned typical synthesis method, J. Appl. Sci. , 45, 47
Many synthetic methods such as those described in 1-485 (1992) and Japanese Patent No. 2583435 have been tried. A compound having a skeleton such as norbornene synthesized by these methods can be used as well.

<Compound (B) Having Two or More Thiol Groups> The above-mentioned “compound (B) having two or more thiol groups” in the shape-memory optical material of the present invention (hereinafter simply referred to as “compound (B)”). .) Is a compound which easily causes an addition reaction to a carbon-carbon double bond contained in a skeleton such as norbornene, and uses a difunctional or higher functional compound to react with the compound (A) to give a polymer. The structure is not particularly limited. Above "Compound (B)"
Specific examples of ethylene glycol dimercaptoacetate, ethylene glycol dimercaptopropionate, 1,4-butanediol dimercaptoacetate, 1,4-butanediol dimercaptopropionate, 1,6-hexanediol dimercapto Acetate, 1,6-hexanediol dimercaptopropionate, trimethylolpropane trimercaptoacetate, trimethylolpropane trimercaptopropionate, pentaerythritol tetramercaptoacetate, pentaerythritol tetramercaptopropionate, pentaerythritol trimercaptoacetate, Pentaerythritol trimercaptopropionate, ditrimethylolpropane tetramercaptoacetate, ditrimethylol B pan tetra mercaptopropionate, dipentaerythritol hexa-mercapto acetate, dipentaerythritol hexa-mercapto propionate, 1,2-di (2-mercaptoethyl thio) -3-mercaptopropane, 2-mercapto-3
Thiohexane-1,6-dithiol, 5,5-bis (mercaptomethyl) -3,7-dithiononane-1,9-dithiol, 2,4,5-tris (mercaptomethyl)-
1,3-dithiolane, 5- (2-mercaptoethyl)-
3,7-dithianonane-1,9-dithiol, 4,8-
Di (mercaptomethyl) -3,6,9-trithioundecane-1,11-dithiol, polysulfide having SH group at the terminal (for example, trade name "Thiocol LP-3" manufactured by Toray Thiokol Company), bis (3-mercapto) Propyl) polydimethylsiloxane, xylylenedithiol, trismercaptomethylbenzene, tetrakismercaptomethylbenzene and the like. These may be used alone,
Moreover, you may use together 2 or more types.

The preferred type of the "compound (B)" varies depending on the purpose of the curable resin composition obtained. For example, when a resin cured product is desired to have high mechanical strength, high elastic modulus and high glass transition temperature, a trifunctional or higher functional thiol compound is suitable. Further, when a flexible resin cured product is required or when it is used as an additive for lowering the elastic modulus of the cured product, 1,6-hexanediol dimercaptopropionate, bis (3 Compounds having a flexible structure such as -mercaptopropyl) polydimethylsiloxane are preferred. Furthermore, high Abbe number,
When high transparency in the near-ultraviolet region is required, it is preferable that the skeleton does not contain an aromatic ring.

In the shape-memory optical material of the present invention, the ratio of the above-mentioned "compound (A)" and "compound (B)" is not particularly limited and may be various according to the required performance and the like. . Usually, the skeleton such as norbornene contained in the "compound (A)" and the "compound (B)"
When converted into the ratio with the thiol group possessed by, the thiol group is 0.5 to 1 equivalent to the skeleton such as norbornene.
It is 2 equivalents, preferably 0.7 to 1.5 equivalents.
By setting the thiol group of the "compound (B)" in the above range, sufficient curing can be achieved, and strength,
It is preferable because it is possible to prevent deterioration of heat resistance and coloration of a cured product.

In the shape-memory optical material of the present invention, the method for curing the "curable resin composition" containing the "compound (A)" and "compound (B)" is not particularly limited, and is usually Curing is performed by heating, or irradiation with active energy rays such as ultraviolet rays. For heat curing,
A desirable curing temperature is 50 ° C to 200 ° C, more preferably 70 ° C to 180 ° C. If the temperature is lower than 50 ° C, the glass transition temperature of the obtained cured product is too low and it is deformed depending on the temperature such as summer, which is not preferable. On the other hand, the curing temperature is 2
If the temperature exceeds 00 ° C, the resin tends to deteriorate due to thermal decomposition,
It is not preferable because it is likely to be discolored or lose its transparency. Further, the curing can be promoted by adding a thermal radical generator such as a peroxide or an azo compound. Other,
A method of adding a photoradical generator and curing the enethiol reaction with light such as ultraviolet rays has been proposed in Japanese Patent No. 2583435 and the like, but a compound that generates radicals by light necessarily emits light of a specific wavelength. It has a strong absorbing property. Therefore, it is preferable that the use of such additives is minimized. Further, it is necessary to use a material that does not absorb the wavelength of light to be transmitted.

<Method for producing optical component of the present invention> The above-mentioned "curable resin composition" used in the method for producing an optical component of the present invention means that functional groups are bound to each other by heating or irradiation with active energy rays such as ultraviolet rays. Is a three-dimensionally cross-linked network polymer which is transparent to light of the wavelength that is going to pass through. In addition, when an external force is applied in the temperature range above the glass transition temperature, the resin is damaged or deforms without causing discoloration or turbidity, and the external force is removed after lowering the temperature below the glass transition temperature in the deformed state. Can retain the deformed state, and when the resin in the deformed state is heated again above the glass transition temperature, it has the property of returning to the initial shape without applying any force during heating (hereinafter This property is described as "shape memory").

The "curable resin composition" in the method for producing an optical component of the present invention preferably has a glass transition temperature of 50 ° C to 200 ° C, more preferably 60 ° C to 60 ° C. It is 150 ° C. The reason is that if the resin cured product has a glass transition temperature in such a temperature range, a heat source necessary for heating, such as a hair dryer, hot water, radiant heat of flame, soldering iron, iron, etc., can be easily obtained. is there. Further, a curable resin having a glass transition temperature of less than 50 ° C. is not preferable because its optical characteristics are apt to change when the temperature is high such as in summer, and it is deformed in some cases.
If the temperature is higher than 00 ° C, the resin will oxidize while heating at high temperature,
It is also not preferable because it is easily deteriorated due to thermal decomposition and is likely to be colored.

The "curable resin composition" that can be preferably used in the method for producing an optical component of the present invention is not particularly limited as long as the resin cured product has a glass transition temperature of 50 ° C to 200 ° C. Examples thereof include epoxy resin, (meth) acrylate resin, diallyl phthalate resin, silicone resin, urethane resin, melamine resin, phenol resin, maleimide resin and the like. However, few of these resins can transmit a wide range of light wavelengths, and the usable wavelengths are limited. Therefore, the resin that can be most preferably used in the method for producing an optical component of the present invention is the transparent curable resin described below.

That is, the above "curable resin composition" in the method for producing an optical component of the present invention is preferably a compound (A) having two or more groups represented by the above formula (1),
A curable resin composition comprising a compound (B) having two or more thiol groups. And the above "compound (A)"
Is a compound having a skeleton such as norbornene described above, and specifically, a compound represented by the above formula (2) or (3) is exemplified. In addition, specific examples of the compound represented by the above formula (3) include compounds represented by the above formulas (5) to (8). The details of the above-mentioned "compound (A)" and "compound (B)" constituting the above "curable resin resin" in the method for producing an optical component of the present invention are described above in "Compound (A)" and "Compound". This is as described in the section (B).

In the steps of the method of manufacturing an optical component of the present invention, the above-mentioned "initial shape" may refer to the whole formed by resin, or may indicate a part thereof. This is because the step of deforming by heating and restoring the shape by reheating in the manufacturing process of the present invention can be applied to a part of the molded part by limiting the heating range. In addition, in the above process, the above “initial shape”
Can be arbitrarily set depending on the shape of the mold used for curing the resin. Further, after curing, it can be formed in advance by a method such as cutting and polishing. In the method for manufacturing an optical component of the present invention, after the above step, if necessary, a restoring step of returning to the initial shape immediately after curing by reheating may be performed, or further, if necessary, the above It is also possible to go through the steps and the step of repeating the above steps.

The method of manufacturing an optical component according to the present invention is applied when it is necessary to pass a component used for transmitting light through a narrow portion when assembling an optical device or the like, attaching, connecting, or maintaining an optical communication device. And so on. For example, when it is necessary to pass an optical waveguide through an elongated hole and fold a component before and after the optical waveguide to deform it into a crank shape, normally, at least one bonding step such as bonding is required. There are two possible ways to do this. The first method is, for example, that a transparent part molded in a crank shape in advance is made of resin, and is straightened while being heated and then cooled to keep the straight state and then passed through a hole, and then hot air or the like. It is a method of returning to the crank shape which is the shape that was remembered by heating with. The second method is a method in which a resin-made transparent component formed in a linear shape is passed through a hole, heated and deformed, and then cooled. The first method is effective when the hands or tools etc. do not directly reach the place to be deformed, and the second method is when the transparent resin parts are once attached and then the transparent resin parts are pulled out again and repeatedly used. Suitable for Further, any of the methods is preferable because it does not require a skillful joining step.

The method for producing an optical component of the present invention has been completed without the need for skilled work such as cutting or joining transparent components that transmit light when producing and assembling an optical component having a complicated shape. It is a manufacturing method with little loss of light when passing light through the parts and with excellent reproducibility. The reason why such a process is possible is that the curable resin used in the method for manufacturing an optical component of the present invention remembers the shape stored in advance, and easily returns to the original shape by applying no special force by heating. This is because of its nature. Further, a resin cured product obtained by curing a composition comprising a norbornene compound and a thiol compound, which is a resin that can be preferably used in the present invention, has a shape memory property and a wide range from the visible light region to the near ultraviolet region. It has excellent properties as a resin for optical parts, such as high light resistance because the norbornene skeleton has high hydrophobicity. Therefore, the optical component of the present invention manufactured by using the method for manufacturing an optical component of the present invention can exhibit excellent characteristics as compared with the conventional optical component.

In the method for producing an optical component of the present invention, a monofunctional norbornene compound or a monofunctional thiol compound is used for the purpose of decreasing the viscosity of the curable resin composition or adjusting the elastic modulus of the cured resin composition. The compounds can be used in combination. In this case, the ratio of the skeleton having a skeleton such as norbornene to the thiol group is preferably adjusted so as to be the above ratio.

The curable resin composition preferably used in the method for producing an optical component of the present invention contains an antioxidant, a dye, a pigment, a filler, a light scattering agent, an ultraviolet absorber, a leveling agent, a release agent and the like. It can be added. It is preferable to add the filler and the like within a range that does not impair the transparency. still,
The light-scattering agent mentioned here is fine particles or the like added to scatter light in order to improve visibility at the light outlet when used for display parts and the like. Further, the curable resin composition that can be preferably used in the method for producing an optical component of the present invention includes a silane coupling agent, a titanium coupling agent, and the like, if necessary, for the purpose of improving the adhesive force to a metal. A coupling agent is added and used in combination. Among these silane coupling agents, a silane coupling agent having an epoxy group, an amino group, a mercapto group, or a carbon-carbon double bond is preferable because it has an effect of improving the adhesion with a metal or the like.

The optical component of the present invention is obtained by heating and curing the resin composition for an optical component of the present invention, and has excellent transparency and water resistance. The optical component of the present invention makes use of its transparency, so that a light emitting diode, various lenses, prisms, mirrors, recording disks, light guide plates, optical waveguides, optical fibers, color filters for liquid crystals, transparent coating films for optical materials, and optical components It can be used as an adhesive or the like. In particular, since it has a high transmittance for light having a short wavelength in the blue to near-ultraviolet region, it can be preferably used as a coating material for an information recording medium, a pickup lens, and its peripheral material.

In the shape memory optical material of the present invention and the optical component of the present invention, the glass transition temperature is preferably 5
The temperature is 0 ° C or higher, more preferably 60 ° C or higher, and further preferably 70 ° C or higher. The wavelength at which the light transmittance is 50% measured by the measuring method of the embodiment is preferably 350.
nm, more preferably 330 nm, even more preferably 32
It is 0 nm. Further, the water absorption rate measured by the measuring method of the example is preferably 0.25% or less, more preferably 0.20% or less, still more preferably 0.16% or less. Moreover, in the shape-memory optical material of the present invention and the optical component of the present invention, various combinations of the above characteristic values can be used.

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples. It should be noted that the present invention is not limited to the following specific examples, and various modified examples can be made according to the purpose and application. 1. Synthesis of Polyfunctional Norbornene Compound (Synthesis Example 1) 10 equipped with thermometer, Dimroth, and stirrer
Dicyclopentadiene dimethanol diacrylate ester (manufactured by Kyoeisha Chemical Co., Ltd.,
Product name "Light acrylate DCP-A") 30g
(0.099 mol) was charged, and 26.1 g (0.1%) of cyclopentadiene obtained by previously decomposing dicyclopentadiene at 150 ° C. with stirring at room temperature.
(39 mol) was added dropwise over 30 minutes. After stirring for 20 hours as it was, the content was transferred to a 100 ml round-bottomed flask, and the cyclopentadiene remaining without reaction was distilled off under reduced pressure. Then, the residual components in the flask were analyzed by NMR. The result is shown in FIG. The NMR measurement conditions were 270 MHz proton NMR, the solvent was deuterated chloroform, the measurement temperature was room temperature, and the reference substance was tetramethylsilane (TMS).

In FIG. 1, the raw materials 5.8 to 6.
The peak of the proton bound to C = C of the acryloyl group around 5 ppm disappeared, and a new peak of 5.9-6.2 ppm was obtained.
A proton of the double bond portion of norbornene appeared in the vicinity, and a proton at the bridgehead position of norbornene was confirmed in the vicinity of 2.8 to 3 ppm. From these results, it was confirmed that cyclopentadiene was added to the acryloyl group of the raw material by the Diels-Alder reaction to generate dinorbornenecarboxylate of dicyclopentadiene dimethanol having a norbornene skeleton.

(Synthesis Example 2) 30 g (0.085 mo) of pentaerythritol tetraacrylate (trade name "Aronix M450" manufactured by Toagosei Co., Ltd.) was placed in a 100 ml three-necked flask equipped with a thermometer, a Dimroth and a stirrer.
1) was charged and 49.5 g (0.75 mol) of cyclopentadiene obtained by previously decomposing dicyclopentadiene at 150 ° C. with stirring at room temperature was used.
It dripped over minutes. After stirring for 20 hours as it was, the content was transferred to a 100 ml round-bottomed flask, and the cyclopentadiene remaining without reaction was distilled off under reduced pressure. Then, the residual components in the flask were analyzed by NMR. The result is shown in FIG. The measurement conditions of NMR are the same as those in Synthesis Example 1 above.
Is the same as. From FIG. 2, as in the above-described Synthesis Example 1,
It was confirmed to be pentaerythritol tetranorbornene carboxylate in which cyclopentadiene was added to the acryloyl group of the raw material by the Diels-Alder reaction to form a norbornene skeleton.

2. Preparation of Resin Composition for Optical Parts and Synthesis and Performance Evaluation of Cured Resin (Example 1) Pentaerythritol tetra (3-mercaptopropionate) 11.2 g on 20 g of the polyfunctional norbornene compound obtained in Synthesis Example 1 above. Was added and mixed by stirring to prepare a curable resin composition. Next, the curable resin composition was defoamed under reduced pressure, poured into a fluororesin mold placed on a glass plate, and the glass plate was placed on the mold and covered. This is sandwiched between the hot plates of a heat press machine and 10 kg /
Heating was performed at 100 ° C. for 30 minutes while applying a pressure of cm ² , the temperature was further raised to 150 ° C., and pressure heating was continued for 1 hour to complete curing of the resin. Then, the cured resin was removed from the mold to obtain a cured resin product of Example 1.

Example 2 To 20 g of the polyfunctional norbornene compound obtained in Synthesis Example 2 above, 15.8 g of pentaerythritol tetra (3-mercaptopropionate) was added and mixed with stirring to prepare a curable resin composition. did. next,
Curing of the resin was completed using the resin composition in the same manner as in Example 1 above. Then, the cured resin was removed from the mold to obtain a cured resin product of Example 2.

(Comparative Example 1) Dicyclopentadiene dimethanol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Light Acrylate DCP-A") 20 g was mixed with 16.1 g of pentaerythritol tetra (3-mercaptopropionate). In addition, the mixture was stirred and mixed to prepare a curable resin composition. Next, the curing of the resin was completed using the curable resin composition in the same manner as in Example 1 above. Then, the cured resin was removed from the mold to obtain a cured resin product of Comparative Example 1. The resin cured product of Comparative Example 1 was rubber-like at room temperature.

Comparative Example 2 A commercially available uncolored polymethylmethacrylate plate was used. Comparative Example 2 had a poor curability and was rubber-like.

3. Performance Evaluation of Resin Cured Products of Examples 1-2 and Comparative Examples 1-2 The performance of each resin cured product of Examples 1-2 and Comparative Example 1 and the resin of Comparative Example 2 was evaluated by the following method. .
The results are shown in Table 1 below. Since the resin cured product of Comparative Example 1 had stickiness and poor curability, the water absorption rate was not measured and the light transmittance was measured by a spectrophotometer. Similarly, Comparative Example 2 was poor in curability and was rubbery, so that the water absorption rate was not evaluated.

Glass transition temperature Using a dynamic viscoelasticity measuring device “DMS6100” manufactured by Seiko Instruments Inc., a temperature rising rate of 4 ° C./mi
The measurement was performed at n and a frequency of 10 Hz. Measured tan
The vertex temperature on the highest temperature side in the δ curve was defined as the glass transition temperature (° C) of the resin. Water absorption The cured resin products of Examples 1-2 and Comparative Examples 1-2 have 5 sides.
cm square and 2 mm thick test piece
The sample was left to stand in the oven for 24 hours to be dried, and the weight when dried was measured. Next, the test piece was placed in distilled water kept at 23 ° C and
After soaking for a period of time, water on the surface was wiped off and the weight after water absorption was measured. The water absorption rate (%) was determined by calculating the weight increase rate (%) from both measured values. Light Transmittance A resin cured product having a thickness of 1 mm prepared using the resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 was used as a test piece.
Shimadzu Corporation spectrophotometer "UV-2400P
C ”was used to measure the light transmittance of the test piece at a wavelength of 190 to 800 nm. The measurement was performed by operating from a long wavelength to a short wavelength, and the light transmittance was evaluated as the wavelength (nm) at the time when the light transmittance first cuts 50%.

Shape memory property In order to confirm that the manufacturing method of the present invention is possible,
The shape memory properties (workability) were compared and examined by the method shown in FIG. In each of Examples 1 and 2 and Comparative Example 1, a 2 mm-thick mold used at the time of curing was preliminarily hollowed into a crank shape having a width of 2 mm, and a crank-shaped resin molded product was obtained by curing. In Comparative Example 2, a resin plate having a thickness of 2 mm was cut into the same crank shape. The two bent portions of the crank shape were curved, and the distance between the bent portions was about 15 mm. These crank-shaped test specimens are shown in Figure 3 which illustrates the process.

Then, the molded crank-shaped resin was heated to a temperature equal to or higher than the glass transition temperature to be expanded into a rod shape, and then cooled to fix the rod shape. After passing this through a glass tube having a hole diameter of about 3 mm and a length of 10 mm, it was observed whether or not it was returned to the original crank shape by heating again to the glass transition temperature or higher and further cooling to room temperature. A rod-shaped test piece is shown in FIG. 3, and a glass tube for inserting the same is also shown in FIG. A specimen that has been returned to its original shape while still passing through the glass tube is also indicated by. : Represents a test piece previously formed into a crank shape. : Represents a test piece deformed into a rod shape by applying force while heating above the glass transition temperature of the resin. : Represents a glass tube for inserting a rod-shaped test piece. : Represents a test piece regenerated into the same shape as the original one by reheating above the glass transition temperature without applying external force to.

[0049]

[Table 1]

4. Effects of Examples From Table 1, in the resin cured products of Examples 1 and 2, the glass transition temperature was as high as 72 ° C and 101 ° C, and the water absorption rate was as low as 0.12% and 0.15% in the water absorption test. It is understood that it shows. Further, in the light transmittance test, the wavelength at the time when the light transmittance of the resin cured product first fell below 50% was 3
It is as low as 10 and 315 nm, and it can be seen that the light transmittance is excellent in a wide wavelength range. Further, in the shape memory test, the original crank shape is restored by reheating. From the above, the resin cured products of Examples 1 and 2 have low hygroscopicity,
It can be seen that it has excellent transparency and excellent shape memory.

On the other hand, as shown in Table 1, the resin cured product of Comparative Example 1 has a glass transition temperature of 26 ° C., which is significantly lower than those of Examples 1 and 2. Further, in the resin cured products of Comparative Examples 1 and 2, the water absorption rate is 0.31% in Comparative Example 2, which is more than double the value of Examples 1 and 2. Further, in the light transmittance test, the light transmittance of the resin cured product was as high as 320 and 375 nm when the light transmittance of 50% was first cut, and the wavelength range where the light transmittance was excellent in a wide wavelength range was narrow. I understand. Also,
Also in the shape memory test, Comparative Example 1 did not become rod-shaped because it was rubber-like at room temperature, and in Comparative Example 2, the resin could be deformed by the first heating. It didn't return to its original shape. From the above, it can be seen that the resin cured products of Comparative Examples 1 and 2 have higher hygroscopicity, inferior transparency, and no shape memory property as compared with Examples 1 and 2.

[Brief description of drawings]

FIG. 1 is a diagram illustrating an H-NMR spectrum of dicyclopentadiene dimethanol di (5-norbornene-2-carboxylate) obtained in Synthesis Example 1.

2 is the H of pentaerythritol tetra (5-norbornene-2-carboxylate) obtained in Synthesis Example 2. FIG.
-A diagram illustrating an NMR spectrum.

FIG. 3 is an explanatory diagram for explaining workability of a cured product in an example.

Claims (7)

[Claims] 1. A curable resin composition containing a compound (A) having two or more groups represented by the following formula (1) and a compound (B) having two or more thiol groups is cured. A shape-memory optical material characterized by being obtained. [Chemical 1] (X is CH ₂ , CH ₃ CH, (CH ₃ ) ₂ C, O or S
And R ¹ is a hydrogen atom, an alkyl group or a carboxyl group or a derivative thereof, and R ² is a hydrogen atom, a cyano group, an alkyl group, a substituted alkyl group or a carboxyl group or a derivative thereof. n is an integer of 0 to 5 and α
Represents a binding site. ) 2. The compound (A) is represented by the following formula (2) or
The shape memory according to claim 1, which is a compound represented by (3).
Optical materials. [Chemical 2] (X is CH_Two, CH_ThreeCH, (CH_Three)_TwoC, O or S
And m¹, M^Two, M ^ThreeAre each independently 0-5
Represents an integer, R⁸, R⁹Are each independently a hydrogen atom or
Represents a methyl group. ) [Chemical 3] (Z is a group represented by the following formula (4), Y is a carbon number 1
~ 5 alkyl groups. In addition, a is an integer of 1 to 4, b
Is an integer of 0 to 2, a'and b'are integers of 0 to 3.
Yes, m is 0 or 1. Furthermore, a + b = 4-m, m
= 1, a '+ b' = 3, and a + a '>
It is 1. Also, in the formula (4), m^FourRepresents an integer from 0 to 5
You Further, in the formula (4), R⁷Is an alkyle having 1 to 4 carbon atoms
Group or a polyalkylene glycol residue, R
¹⁰Represents a hydrogen atom or a methyl group. X is the above formula
It is synonymous with (1). It should be noted that there are two or more in one molecule
Even if the structures of the groups represented by formula (4) are the same,
It may be different. ) [Chemical 4] 3. A curing step of imparting an initial shape by curing a curable resin composition capable of giving a glassy transparent resin cured product at room temperature, and maintaining the temperature above the glass transition temperature of the resin cured product. Then, a deformation step of applying an external force to deform and a deformation holding step of cooling while still deformed, removing the external force, and holding a deformed state different from the initial shape are carried out. 4. The glass transition temperature is 50 ° C. to 200 ° C.
The method for manufacturing an optical component according to claim 3, wherein 5. The curable resin containing the compound (A) having two or more groups represented by the formula (1) and the compound (B) having two or more thiol groups. The method for producing an optical component according to claim 3, which is a composition. 6. The method for producing an optical component according to claim 5, wherein the compound (A) is a compound represented by the formula (2) or (3). 7. An optical component manufactured by using the method for manufacturing an optical material according to claim 3. Description: