JP5401767B2 - Curable composition and optical device - Google Patents

Description

  The present invention relates to a curable composition and an optical device using the same, and more specifically, it can realize adhesion of an optical device over a long period without causing defects such as peeling even in a high temperature environment or a high temperature and high humidity environment. The present invention relates to a curable composition and an optical device using the same.

  Conventionally, ultraviolet curable adhesives have been widely used for bonding optical devices from the viewpoints of transparency, fast curability, and fixability. In particular, acrylic UV curable adhesives have been used for bonding uneven surfaces present in optical devices, but there is a problem that the adhesive strength of the adhesive decreases due to hydrolysis of ester groups. there were. Therefore, in recent years, epoxy / oxetane UV curable adhesives have been used.

  Epoxy / oxetane-based UV-curable adhesives are generally rigid hydrogenated bisphenol A type epoxies to achieve transparency and fixability of optical devices in high-temperature environments or high-temperature and high-humidity environments. A compound is used.

In addition, an epoxy / oxetane ultraviolet curable adhesive uses an onium salt polymerization initiator such as an iodonium salt or a sulfonium salt as a reaction initiator (see Patent Document 1 and Patent Document 2).
WO2005 / 028537 (published March 31, 2005) Japanese Patent Laid-Open No. 11-161136 (released on June 18, 1999)

  However, in the epoxy / oxetane UV curable adhesive having the above-mentioned hydrogenated bisphenol A type epoxy compound, when the cured product is placed in a high temperature environment or a high temperature and high humidity environment, an unreacted cationic polymerization compound , The cured product is further cured. With this further curing, the shrinkage stress acting on the cured product increases.

  Here, in the cured product of the ultraviolet curable adhesive, the flexibility of the cured product is poor, and thus the shrinkage stress cannot be relaxed. For this reason, the said shrinkage stress will be transmitted to the adhesion interface of hardened | cured material. Thereby, there exists a problem that the adhesive force of the said hardened | cured material falls and causes malfunctions, such as peeling.

  Further, since the cationic polymerization compound used in the conventional epoxy / oxetane ultraviolet curable adhesive has low reactivity, an unreacted cationic polymerization compound remains in the cured product. Then, the shrinkage stress increases due to the uncured cationic polymerization compound in a high temperature environment or a high temperature and high humidity environment. In addition, the polymerization initiator reacts with an alkali metal such as Na or K to generate foreign matter. There is a problem that such an increase in shrinkage stress and the generation of foreign matter cause problems such as peeling of the cured product.

  Furthermore, since the onium salt polymerization initiator represented by the above-mentioned Adekaoptomer SP-150 is generally dissolved in a high boiling point solvent, the cured product also contains the high boiling point solvent. . Therefore, when the cured product is placed in a high temperature environment or a high temperature and high humidity environment, the high boiling point solvent serves as a carrier, and the onium salt-based polymerization initiator is diffused into the cured product. And since the hardening | curing of an unreacted cationic polymerization type compound is accelerated over a wide range with the said diffused onium salt type polymerization initiator, the increase in the shrinkage stress of hardened | cured material and generation | occurrence | production of a foreign material are accelerated | stimulated. And thereby, the problem that raise | generates malfunctions, such as peeling of hardened | cured material, arises.

  The present invention has been made in view of the above-described problems, and the object thereof is to realize adhesion of an optical device over a long period of time without causing defects such as peeling even in a high temperature environment or a high temperature and high humidity environment. It is providing a curable composition and an optical device using the same.

  As a result of intensive studies in view of the above problems, the present inventor obtained by curing a curable composition containing (i) a carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound and / or an epoxidized polybutadiene compound as an essential component. Curing is accelerated by having the properties that the cured product has excellent flexibility and adhesiveness, and (ii) blending the curable composition with an alicyclic epoxy compound and an oxetane compound having a hydroxyl group. The amount of uncured product present in the cured product can be reduced, and (iii) by adding an onium salt polymerization initiator not dissolved in a high boiling point solvent as a cationic polymerization agent to the curable composition, This prevents the onium salt polymerization initiator from diffusing into the cured product in an environment or in a high temperature and high humidity environment. It found that can be, and have completed the present invention.

  That is, the curable composition of the present invention includes a carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound (A-1) and / or an epoxidized polybutadiene compound (A-2), (A-1) and a curable composition containing a cationically polymerizable compound (B) other than (A-2), wherein the cured product of the curable composition has a refractive index at 25 ° C. and 589 nm. It is characterized by being 1.40 or more and 1.60 or less.

  According to the above configuration, the flexibility and adhesion of the cured product of the curable composition can be improved by the flexibility and adhesion of the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound and / or the flexibility of the epoxidized polybutadiene compound. Can be improved. Therefore, when the cured product is placed in a high-temperature environment or a high-temperature and high-humidity environment, the increase in shrinkage stress accompanying further curing of the cured product can be mitigated, and the adhesive strength of the cured product to the adherend can be reduced. Decrease can be prevented. For this reason, when the cured product and the adherend are bonded, it is possible to prevent a decrease in the adhesive force of the cured product to the adherend and separation from the adherend. In other words, the hardened | cured material of the said curable composition has the adhesiveness excellent in heat resistance and water resistance with respect to a to-be-adhered body.

  Since the cationic polymerizable compound (B) is excellent in photocurability, the curable composition can be cured more easily.

  Moreover, the member used for an optical device is generally glass with a refractive index of 1.40 to 1.60. Here, since the refractive index at 25 ° C. and 589 nm of the cured product of the curable composition is 1.40 or more and 1.60 or less, the curable composition can be used for an optical device even if it is used for an optical device. The reflected optical signal is not refracted or reflected. Therefore, a high-performance optical device can be produced using the curable composition.

  In the curable composition of the present invention, the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound (A-1) and / or the epoxidized polybutadiene compound (A-2) does not contain a high boiling point solvent. It is preferable.

  The carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound (A-1) and / or the epoxidized polybutadiene compound (A-2) contains a high-boiling solvent, and a cationic polymerization initiator is used for the curable composition. When the cured product is prepared, when the cured product is exposed to a high temperature environment or a high temperature and high humidity environment, the acid generated from the cationic polymerization initiator diffuses into the cured product using the high boiling point solvent as a medium. The diffused acid and the unpolymerized cationic polymerizable compound react to cure the unpolymerized cationic polymerizable compound. This causes a problem that the shrinkage stress of the cured product increases. Furthermore, when the said hardened | cured material is used for the to-be-adhered body containing an alkali metal, the said acid and an alkali metal react and form a salt. This salt causes a problem that the light transmittance of the adherend is deteriorated.

  Here, in the curable composition of the present invention, the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound (A-1) and / or the epoxidized polybutadiene compound (A-2) does not contain a high boiling point solvent. Therefore, the amount of the high boiling point solvent contained in the curable composition can be eliminated or reduced. As a result, when the cured product of the curable composition is exposed to a high-temperature environment or a high-temperature and high-humidity environment, it is possible to prevent the acid from diffusing in the cured product, thereby solving the above problem. I can do it. Therefore, the curable composition of the present invention is very useful in that the light transmittance of the adherend can be maintained. For example, as will be described later, the curable composition of the present invention can be used very effectively as an adhesive for members of optical devices.

  In the curable composition of the present invention, the cationic polymerizable compound (B) is preferably an epoxy compound and / or an oxetane compound. The epoxy compound and oxetane compound are excellent in photocationic polymerizability. Therefore, curing of the curable composition with light can be performed more easily. Further, the cationic polymerizable compound (B) has a low viscosity and is excellent in dilutability of the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound (A-1) or the epoxidized polybutadiene compound (A-2). The viscosity of the composition can be made appropriate.

  In the curable composition of the present invention, the cationic polymerizable compound (B) is preferably an alicyclic epoxy compound and an oxetane compound having a hydroxyl group. Thereby, since hardening occurs cooperatively between an alicyclic epoxy compound and an oxetane compound having a hydroxyl group, hardening of the curable composition can be promoted. As a result, since the amount of the uncured product present in the cured product of the curable composition can be reduced, it is possible to prevent the shrinkage stress from increasing in a high temperature environment or a high temperature and high humidity environment.

  The curable composition of the present invention preferably further contains a cationic polymerization initiator. According to this, since the cationic polymerization initiator is previously contained in the curable composition, it is not necessary to mix the cationic polymerization initiator and the curable composition immediately before curing the curable composition. For this reason, a curable composition can be hardened more simply.

  In the curable composition of the present invention, the cationic polymerization initiator is preferably an onium salt photocationic polymerization initiator. Thereby, the said onium salt type | system | group photocationic polymerization initiator becomes a catalyst, and hardening of a curable composition can be accelerated | stimulated by irradiating light. In addition, corrosive outgas is not generated even in a high temperature environment or a high temperature and high humidity environment. Therefore, even when the curable composition and a metal are bonded, stable bonding can be realized without corroding the metal.

  Moreover, in the curable composition of this invention, it is preferable that the said onium salt type | system | group photocationic polymerization initiator is not melt | dissolving in the high boiling-point solvent. When the onium salt-based photocationic polymerization initiator contains a high-boiling solvent, when the cured product is exposed to a high-temperature environment or a high-temperature and high-humidity environment, the onium salt-based medium is used as the medium. The acid generated from the photocationic polymerization initiator diffuses into the cured product. The diffused acid and the unpolymerized cationic polymerizable compound react to cure the unpolymerized cationic polymerizable compound.

  This causes a problem that the shrinkage stress of the cured product increases. Furthermore, when the said hardened | cured material is used for the to-be-adhered body containing an alkali metal, the said acid and an alkali metal react and form a salt. This salt causes a problem that the light transmittance of the adherend is deteriorated.

  Here, in the curable composition of the present invention, the onium salt-based photocationic polymerization initiator does not contain a high-boiling solvent, so the amount of the high-boiling solvent contained in the curable composition is eliminated or reduced. Can do. As a result, when the cured product of the curable composition is exposed to a high-temperature environment or a high-temperature and high-humidity environment, it is possible to prevent the acid from diffusing in the cured product, thereby solving the above problem. I can do it. Therefore, the curable composition of the present invention is very useful in that the light transmittance of the adherend can be maintained. For example, as will be described later, the curable composition of the present invention can be used very effectively as an adhesive for members of optical devices.

  Moreover, it is preferable that the curable composition of this invention further contains a silane coupling agent. The silane coupling agent has a property of chemically bonding an inorganic material or a metal material and a curable composition or a cured product thereof. Therefore, by including a silane coupling agent in the curable composition of the present invention, the adhesion of the curable composition of the present invention or a cured product thereof to an inorganic material or a metal material can be improved.

  Moreover, in the curable composition of this invention, the thickness of the hardened | cured material of the said curable composition is 100 micrometers, and the light transmittance in 1200 nm or more and 1700 nm or less of the said hardened | cured material is 60% or more and 100% or less. preferable. 1200 nm to 1700 nm is an optical signal wavelength that is suitably used for optical devices such as fiber arrays, WDM modules, and collimator arrays. If the thickness of the cured product is 100 μm and the light transmittance of the cured product at 1200 nm to 1700 nm is 60% or more and 100% or less, the optical signal passing through the cured product is hardly weakened. Can be communicated well. Therefore, a high-performance optical device can be produced using the curable composition.

  Moreover, the optical device of the present invention is characterized by being manufactured using the curable composition. As described above, the cured product of the curable composition has adhesiveness excellent in heat resistance and water resistance to the adherend. And since the said curable composition is used for the said optical device, the said optical device can implement | achieve the outstanding heat resistance and moisture resistance.

  In the optical device of the present invention, the optical device preferably has two or more members. According to this, members can be adhere | attached with the said curable composition. Here, the hardened | cured material of the said curable composition has the adhesiveness excellent in heat resistance and water resistance with respect to a to-be-adhered body. Therefore, it is possible to prevent the members from being separated from each other in a high temperature environment or a high temperature and high humidity environment. Therefore, the optical device can realize excellent heat resistance and moisture resistance.

  In the optical device of the present invention, the material used for the member is preferably an organic material or synthetic quartz. Since the organic material and the synthetic quartz can transmit light, the member can be bonded by irradiating light.

  As described above, the curable composition of the present invention comprises a carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound (A-1) and / or an epoxidized polybutadiene compound (A-2) and the above (A-1). And a cationically polymerizable compound (B) other than (A-2), wherein the cured product of the curable composition has a refractive index of 1.40 or more at 25 ° C. and 589 nm. .60 or less.

  Therefore, the flexibility and adhesiveness of the cured product of the curable composition can be improved by the flexibility and adhesion of the carboxy-terminated butadiene nitrile rubber modified bisphenol A type epoxy compound and / or the flexibility of the epoxidized polybutadiene compound. I can do it. Therefore, when the cured product is placed in a high-temperature environment or a high-temperature and high-humidity environment, the increase in shrinkage stress accompanying further curing of the cured product can be mitigated, and the adhesive strength of the cured product to the adherend can be reduced. There exists an effect that it can prevent falling. Therefore, when the cured product and the adherend are bonded, there is an effect that it is possible to prevent a decrease in the adhesive force of the cured product to the adherend and separation from the adherend.

  Since the cation polymerizable compound (B) is excellent in photocurability, the curable composition can be cured more easily.

  Moreover, the member used for an optical device is generally glass with a refractive index of 1.40 to 1.60. Here, since the refractive index at 25 ° C. and 589 nm of the cured product of the curable composition is 1.40 or more and 1.60 or less, the curable composition can be used for an optical device even if it is used for an optical device. The reflected optical signal is not refracted or reflected. Therefore, it is possible to produce a high-performance optical device using the curable composition.

  Moreover, the optical device of the present invention is manufactured using the curable composition. As described above, the cured product of the curable composition has adhesiveness excellent in heat resistance and water resistance to the adherend. And since the said curable composition is used for the said optical device, there exists an effect that the said optical device can implement | achieve the outstanding heat resistance and moisture resistance.

  The present invention is described in detail below. In addition, all the patent documents described in this specification are used as reference in this specification.

[1: Curable composition]
<Curable composition>
The curable composition of this invention is a composition which produces hardened | cured material by hardening. And the said hardened | cured material has a property which adhere | attaches an adherend and an adherend. That is, the curable composition of the present invention can be used as an adhesive for bonding the adherend and the adherend.

  Specifically, the curable composition of the present invention comprises a carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound (A-1) and / or an epoxidized polybutadiene compound (A-2), and the above (A-1). And a cationically polymerizable compound (B) other than (A-2), and the refractive index of the cured product of the curable composition at 25 ° C. and 589 nm is preferably 1.40. It is 1.60 or less, more preferably 1.42 or more and 1.58 or less, and further preferably 1.45 or more and 1.55 or less. According to said structure, the softness | flexibility of hardened | cured material can be improved by the effect | action of the flexibility and adhesiveness of a carboxy terminal butadiene nitrile rubber modified bisphenol A type epoxy compound, and / or the flexibility of an epoxidized polybutadiene compound. Accordingly, when the curable composition is cured or when the cured product is placed in a high temperature environment or a high temperature and high humidity environment, it is possible to reduce the increase in shrinkage stress of the cured product, and the cured product. It can prevent that the adhesive force with respect to a to-be-adhered body falls. Therefore, it is possible to provide a cured product that does not easily peel from the adherend even in a high temperature environment or a high temperature and high humidity environment.

  Moreover, the member used for an optical device is generally glass with a refractive index of 1.40 to 1.60. Here, since the refractive index at 25 ° C. and 589 nm of the cured product of the curable composition is in the above range, even if the curable composition is used in an optical device, the optical signal used in the optical device is refracted. It is not allowed to be reflected or reflected. Therefore, it is possible to produce a high-performance optical device using the curable composition.

  In this specification, “under a high temperature environment” means an environment having a temperature of 60 ° C. or higher, and “under a high temperature and high humidity environment” means that the temperature is 60 ° C. or higher and the humidity is 60 RH% or higher. It is a certain environment. The “shrinkage stress” refers to a force that is generated in the cured product and tends to shrink. In addition, the “adhered body” is a member that can be bonded using the curable composition of the present invention, and examples thereof include, but are not limited to, an optical device member described later. .

  The said carboxy terminal butadiene nitrile rubber modified bisphenol A type epoxy compound is an addition reaction product of a carboxy terminal butadiene nitrile rubber and a bisphenol A type epoxy resin. Although the manufacturing method is not specifically limited, For example, it can manufacture by addition reaction of a carboxy terminal butadiene nitrile rubber and a bisphenol A type epoxy resin. Moreover, as said carboxy terminal butadiene nitrile rubber modified bisphenol A type epoxy compound, for example, Epicron TSR-960 (manufactured by Dainippon Ink & Chemicals, Inc.) can be used.

  The addition ratio of the carboxy-terminated butadiene nitrile rubber-modified bisphenol A-type epoxy compound is not particularly limited, but is preferably 5 to 65 parts by weight, more preferably 15 to 55 parts by weight with respect to 100 parts by weight of the curable composition. Parts, more preferably 25 parts by weight to 45 parts by weight.

  Although the manufacturing method of the said epoxidized polybutadiene compound is not specifically limited, For example, it can manufacture by performing addition reaction of a hydroxyl-terminated polybutadiene and a bisphenol A type epoxy resin. Moreover, as said epoxidized polybutadiene compound, EPB-13 (made by Nippon Soda Co., Ltd.) etc. can be used, for example.

  The addition ratio of the epoxidized polybutadiene compound is not particularly limited, but is preferably 5 to 65 parts by weight, more preferably 15 to 55 parts by weight, and still more preferably 25 parts by weight with respect to 100 parts by weight of the curable composition. Part to 45 parts by weight.

  Although it does not specifically limit as a cationically polymerizable compound (B), For example, conventionally well-known cationically polymerizable compounds, such as an epoxy compound or an oxetane compound, are mentioned. Cationic polymerization can be further promoted by incorporating the cationic polymerizable compound (B) into the curable composition.

  The epoxy compound is a general term for compounds having at least one epoxy group in the molecule, and examples thereof include, but are not limited to, alicyclic epoxy compounds and aromatic epoxy compounds.

  An alicyclic epoxy compound is a compound having an alicyclic epoxy group in the molecule. Here, the alicyclic epoxy group is a general term for groups that form an epoxy bond in an alicyclic structure, such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2 -(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl- Examples include, but are not limited to, 3,4-epoxycyclohexanecarboxylate. These alicyclic epoxy compounds can be used alone or in combination of two or more.

  The aromatic epoxy compound is a compound having at least one epoxy group and at least one aromatic ring. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, halogenated bisphenol A type epoxy. Examples include, but are not limited to, resins. These aromatic epoxy compounds can be used alone or in combination of two or more.

  The addition ratio of the epoxy compound is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, and further preferably 15 to 35 parts by weight with respect to 100 parts by weight of the curable composition. is there.

  The oxetane compound is a general term for compounds having at least one oxetane ring in the molecule. For example, 3,3-dimethyloxetane, 3,3-bis (chloromethyl) oxetane, 2-hydroxymethyloxetane, 3- Methyl-3-oxetanemethanol, 3-methyl-3-methoxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, resorcinol bis (3-methyl-3-oxetanylethyl) ether, m-xylylenebis (3-ethyl-3) -Oxetanyl ethyl ether) and the like, but is not limited thereto.

  Furthermore, the oxetane compound contained in the curable composition of the present invention is more preferably an oxetane compound having a hydroxyl group. Examples of such oxetane compounds include, but are not limited to, 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-oxetanemethanol, and the like. These oxetane compounds can be used alone or in combination of two or more.

  The addition ratio of the oxetane compound is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, and further preferably 15 to 35 parts by weight with respect to 100 parts by weight of the curable composition. .

  The above-mentioned cationically polymerizable compounds such as epoxy compounds and oxetane compounds can be used alone or in combination of two or more. In particular, it is preferable to use an alicyclic epoxy compound and an oxetane compound having a hydroxyl group in combination. Thereby, since hardening occurs cooperatively between the alicyclic epoxy compound and the oxetane compound having a hydroxyl group, hardening of the curable composition can be promoted. As a result, since the amount of the uncured product present in the cured product can be reduced, it is possible to prevent the shrinkage stress from increasing in a high temperature environment or a high temperature and high humidity environment.

  In addition, conventionally known cationically polymerizable compounds generally do not contain a high-boiling solvent. Therefore, by using such a cationically polymerizable compound, a curable composition that does not contain a high-boiling solvent. Can be provided.

  Since the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound, the epoxidized polybutadiene compound, and the cationically polymerizable compound (B) are cationically polymerizable compounds, the method for curing the curable composition of the present invention includes a cation. Polymerization can be suitably used. When performing cationic polymerization, it is preferable to use a cationic polymerization initiator such as a photo cationic polymerization initiator or a thermal cationic polymerization agent. Thereby, the said cationic polymerization can be activated and hardening of the curable composition of this invention can be accelerated | stimulated.

  The curable composition and the cationic polymerization initiator may be mixed when the curable composition is cured. That is, the cationic polymerization initiator may be previously contained in the curable composition, or the cationic polymerization initiator and the curable composition may be separately provided. When the cationic polymerization initiator and the curable composition are separated, the cationic polymerization initiator is mixed with the curable composition by a conventionally known method, and then the curable composition is added by applying light or heat. Harden.

  The photocationic polymerization initiator is a compound that is cleaved by the action of light energy and releases an acid. Examples thereof include various onium salt photocationic polymerization initiators such as diazonium salts, iodonium salts, and sulfonium salts. In the onium salt photocationic polymerization initiator, the cation moiety is preferably aromatic sulfonium. By using these cations, stable cationic polymerization can be performed.

In the onium salt photocationic polymerization initiator, the anion moiety is at least selected from the group consisting of BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , and B (C ₆ F ₅ ) ₄ ^−. One or more anions are preferred. The anion is excellent in curing reactivity and can further accelerate the curing reaction by light of the curable composition.

  Specific examples of the onium salt-based photocationic polymerization initiator include triphenylsulfonium hexafluorophosphate, boron tetrafluoride phenyldiazonium salt, phosphorus hexafluoride diphenyliodonium salt, and antimony hexafluoride diphenyliodonium. Salt, tri-4-methylphenylsulfonium salt of arsenic hexafluoride, tri-4-methylphenylsulfonium salt of antimony tetrafluoride, phenylthiopyridium salt, CD-1012 (trade name: manufactured by SARTOMER), PCI- Examples include, but are not limited to, 019, PCI-021 (trade name: manufactured by Nippon Kayaku Co., Ltd.), Optomer SP-150, Optomer SP-170 (trade name: manufactured by ADEKA), and the like. These may be used alone or in combination of two or more, and may be used in combination with one or more thermal cationic polymerization initiators.

  The addition ratio of the cationic photopolymerization initiator is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, and even more preferably 1.5 parts by weight with respect to 100 parts by weight of the curable composition. Parts to 3 parts by weight.

  The thermal cationic polymerization initiator is a compound that is cleaved by the action of heat, that is, an increase in temperature, and releases an acid. For example, various onium salt-based thermal cationic polymerization initiators can be mentioned.

  As the above onium salt-based thermal cationic polymerization initiator, specifically, Adeka Opton CP-66, CP-77 (trade name: manufactured by ADEKA), Sun-Aid SI-60L, SI-80L, SI-100L, SI-110L SI-180L (trade name: manufactured by Sanshin Chemical Co., Ltd.), CI-2920, CI-2921, CI-2946, CI-2939, CI-2624, CI-2064 (trade name: manufactured by Nippon Soda Co., Ltd.), FC-520 (trade name: manufactured by 3M) and the like can be used, and these can be used alone or in combination of two or more, and can be used in combination with one or more photocationic polymerization initiators. it can.

  The addition ratio of the thermal cationic polymerization initiator is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, and even more preferably 1.5 parts by weight with respect to 100 parts by weight of the curable composition. Parts to 3 parts by weight.

  Here, in the curable composition of the present invention, at least one compound selected from the group consisting of the photocationic polymerization initiator, the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound, and the epoxidized polybutadiene compound has a high boiling point. It is preferable not to contain a solvent, and it is most preferable that the cationic polymerization initiator, the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound, and the epoxidized polybutadiene compound do not contain a high boiling point solvent. According to this, the curable composition which does not contain a high boiling point solvent can be provided.

  Cationic polymerization initiators such as the above-mentioned photocationic polymerization initiator and thermal cationic polymerization initiator are generally dissolved in a high boiling point solvent. When the cationic polymerization initiator dissolved in such a high boiling point solvent is used, the high boiling point solvent is also contained in the cured product of the curable composition. When the cured product is placed in a high-temperature environment or a high-temperature and high-humidity environment, the acid generated from the cationic polymerization initiator diffuses into the cured product using the high-boiling solvent as a medium. The diffused acid and the unpolymerized cationic polymerizable compound react to cure the unpolymerized cationic polymerizable compound. This causes a problem that the shrinkage stress of the cured product increases.

  Moreover, when the said curable composition is used for the to-be-adhered body which has an alkali metal, the said acid and an alkali metal form a salt. Therefore, the problem that the light transmittance of the to-be-adhered body containing an alkali metal will deteriorate by using the conventional curable composition is caused.

  However, in the curable composition of the present invention, since there is no high boiling point solvent in the cured product of the curable composition, the cured product is cured when placed in a high temperature environment or a high temperature and high humidity environment. Since the acid can be prevented from diffusing in the object, the above problem can be solved. Therefore, the curable composition of the present invention is very useful in that the light transmittance of the adherend can be maintained. For example, as will be described later, the curable composition of the present invention can be used very effectively as an adhesive for members of optical devices.

  The above “carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound not containing a high boiling point solvent” uses, for example, a high boiling point solvent when performing an addition reaction between a carboxy-terminated butadiene nitrile rubber and a bisphenol A type epoxy resin. Without it you can get it. The “epoxidized polybutadiene compound not containing a high-boiling solvent” can be obtained unless a high-boiling solvent is used when an oxidation reaction of polybutadiene is performed.

  The high boiling point solvent is a solvent having a boiling point of 180 ° C. or higher, and examples thereof include propylene carbonate, γ-butyrolactone, and ethylene glycol, but are not limited thereto. In addition, “not dissolved in a high-boiling solvent” means that the curable composition is heated at 250 ° C. for 15 minutes by the headspace method and subjected to gas chromatography analysis using an internal standard to determine the content of the high-boiling solvent. When measured, it is preferably 0 to 1 part by weight, more preferably 0 to 0.5 part by weight, and still more preferably 0 to 0.3 part by weight with respect to 100 parts by weight of the curable composition. It means that a high boiling point solvent is contained. The above-mentioned headspace method is described in, for example, “JEOL MS Data Sheet, MS Tips”, “Simultaneous Analysis of 1,4-Dioxane and Volatile Organic Compounds by Purge & Trap-GC / MS” 081, JEOL Ltd., Analytical Instruments Applied Research Group, 2006, Internet <URL: http: // www. jeol. co. jp / technical / ai / ms / mstips-081 / index. However, the present invention is not limited to this.

  In the curable composition of the present invention, the thickness of the cured product of the curable composition is preferably 100 μm, and the light transmittance of the cured product from 1200 nm to 1700 nm is preferably from 60% to 100%. 80% or more and 100% or less is more preferable, and 90% or more and 100% or less is more preferable. 1200 nm to 1700 nm is an optical signal wavelength that is suitably used for optical devices such as fiber arrays, WDM modules, and collimator arrays. If the thickness of the cured product is 100 μm and the light transmittance of the cured product at 1200 nm to 1700 nm is 60% or more and 100% or less, the optical signal passing through the cured product is hardly weakened. Can be communicated well. Therefore, a high-performance optical device can be produced using the curable composition.

  The curable composition in which the light transmittance at 1200 nm to 1700 nm of the cured product is in the above range is not particularly limited. For example, a cationic polymerization initiator, a carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound (A-1 ) And / or an epoxidized polybutadiene compound (A-2) not containing a high boiling point solvent and a cationically polymerizable compound (B) can be obtained by mixing so that air does not enter.

  Further, the curable composition of the present invention may further contain (1) an activator of a cationic polymerization initiator, (2) a silane coupling agent, (3) an inorganic filler, and the like as other components. good. The above (1) to (3) will be described below.

(1) Activator for Cationic Polymerization Initiator The activity of the cationic polymerization initiator can be increased by using an activator for the cationic polymerization initiator. Therefore, the curing of the curable composition of the present invention can be further promoted by adding the cationic polymerization initiator and the cationic polymerization initiator activator to the curable composition of the present invention. Examples of the activator of the cationic polymerization initiator include, but are not limited to, a sensitizer and a radical polymerization initiator. Further, the sensitizer and the radical polymerization initiator may be used separately or in combination.

  Examples of the sensitizer include, but are not limited to, pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavine. These sensitizers can be used alone or in combination of two or more. The addition ratio of the sensitizer is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, and even more preferably 1.5 parts by weight with respect to 100 parts by weight of the curable composition. ~ 3 parts by weight.

  Examples of the radical polymerization initiator include thioxanthones such as benzophenone, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2,4-dichlorothioxanthone, and benzoin such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Ethers, benzyldimethylketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) ) -2-hydroxy-2-methylpropan-1-one and the like. These radical initiators can be used alone or in combination of two or more. The addition ratio of the radical polymerization initiator is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, and even more preferably 1.5 parts by weight with respect to 100 parts by weight of the curable composition. Parts to 3 parts by weight.

  The cation polymerization initiator activator generally does not contain a high-boiling solvent. Therefore, it is possible to provide a curable composition containing no high boiling point solvent by using the activator of the cationic polymerization initiator.

(2) Silane Coupling Agent A silane coupling agent has a property of chemically bonding an inorganic material or a metal material and a curable composition or a cured product thereof. Therefore, by including a silane coupling agent in the curable composition of the present invention, the adhesion of the curable composition of the present invention or the cured product to an inorganic material or a metal material can be improved.

  Although it does not specifically limit as a silane coupling agent, For example, the following silane coupling agents can be used: (gamma) -glycidoxypropyl trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , Vinyltrimethoxysilane, P-styryltrimethoxysilane, tetramethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane. As the silane coupling agent, a silane coupling agent having an epoxy group is preferable. This is because the epoxy group can easily bind the inorganic material or the metal material to the curable composition or the cured product thereof. In addition, a silane coupling agent can be used individually or in combination of 2 or more types.

  Among the silane coupling agents exemplified above, γ-glycidoxypropyltrimethoxysilane, because of the stronger chemical bond between the inorganic material or metal material and the curable composition or cured product thereof, And / or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is most preferred.

  The addition ratio of the silane coupling agent is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight, and further preferably 3 to 8 parts by weight with respect to 100 parts by weight of the curable composition. Parts by weight.

  The silane coupling agent generally does not contain a high boiling point solvent. Therefore, by using the activator for the silane coupling agent, a curable composition containing no high boiling point solvent can be provided.

(3) Inorganic filler By containing an inorganic filler in the curable composition of the present invention, not only the viscosity of the curable composition or the volumetric shrinkage during curing can be reduced, but also the curable composition. The thermal durability of the cured product can also be improved. Although it does not specifically limit as said inorganic filler, For example, although silica, an alumina, a calcium carbonate, a talc, a titanium oxide etc. are mentioned, it is not limited to these. These inorganic fillers can be used alone or in combination of two or more.

  The addition ratio of the inorganic filler is preferably 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, and further preferably 30 to 60 parts by weight with respect to 100 parts by weight of the curable composition. is there.

  Moreover, the said inorganic filler generally does not contain the high boiling point solvent. Therefore, a curable composition containing no high-boiling solvent can be provided by using the above-mentioned inorganic filler activator.

<Method for producing curable composition>
The curable composition of the present invention is mixed using, for example, a conventionally known method such as stirring the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound and / or epoxidized polybutadiene compound and a cationic polymerization initiator. Can be manufactured. Furthermore, you may mix each component of said (1)-(3) as needed.

  Since the cured product of the curable composition of the present invention is excellent in flexibility as described above, it has characteristics such as being difficult to peel from a member in a high temperature environment or a high temperature and high humidity environment. Therefore, the curable composition of the present invention makes use of such properties, such as adhesives for displays for optical devices and liquid crystals, paints, coating agents for various materials such as metals and plastics, sealing agents, and sealing. It can be used as an agent.

  Below, the optical device using the curable composition of this invention is demonstrated.

[2: Optical device]
<Optical device>
The optical device of the present invention is manufactured using the curable composition of the present invention described above. “Using the curable composition of the present invention” is not particularly limited. For example, the curable composition of the present invention is used for coating the member of the optical device of the present invention, or the optical device of the present invention is used. It is used for adhesion of members. Moreover, if the optical device of this invention has two or more members, members can be adhere | attached using the said curable composition.

  The above-mentioned “use the curable composition of the present invention for coating the member of the optical device of the present invention” means, for example, that the curable composition of the present invention is used by using a conventionally known method such as a spin coating method. Applying to a member. Although it does not specifically limit as a member of an optical device, For example, the member using the material which can apply the curable composition of this invention can be mentioned.

  Moreover, when bonding members using the curable composition of this invention, a curable composition may be used for adhesion | attachment of the member in which only the same material is used, and a different material is used. It may be used for adhesion of existing members.

  Examples of materials to which the curable composition of the present invention can be applied include quartz, organic materials, metals, and the like, but are not limited thereto. Examples of the quartz include, but are not limited to, synthetic quartz, fused quartz, and glass. Examples of the organic material include, but are not limited to, acrylic, polycarbonate, polyester, polyurethane, silicone, polypropylene, polyphenylene terephthalate, polybutylene terephthalate, and polyvinyl chloride. Examples of the metal include, but are not limited to, aluminum, stainless steel, electrodeposition coated steel, soft iron steel, brass steel, carbon steel, titanium, lead, vinyl chloride steel, and aluminum magnesium steel.

  In a conventional curable composition, a photocationic polymerization initiator and an alkali metal contained therein form a salt. For this reason, an opaque foreign matter is generated between the cured product of the conventional curable composition and the member, and the cured product and the member are peeled off, and the light transmittance between the cured product and the member is deteriorated. was there. On the other hand, when the curable composition of the present invention does not contain a high-boiling solvent, as described above, the acid released from the photocationic polymerization initiator can be prevented from diffusing into the cured product. , Can solve such problems. Therefore, the said curable composition is very useful also in the aspect which can suppress peeling with hardened | cured material and a member, and can maintain the light transmittance of hardened | cured material and a member.

  In addition, when the curable composition of this invention contains a photocationic polymerization initiator, a curable composition will harden | cure by irradiating light to a curable composition, and members will adhere by this hardening. I can do it. Therefore, at least one of the members that can be bonded is a material having a material that can transmit light, such as quartz or an organic material (hereinafter referred to as “light-transmitting material”). Is preferably provided. Thereby, light can be irradiated to a curable composition through a light transmissive material. Examples of the light transmissive material include, but are not limited to, synthetic quartz, fused quartz, glass, acrylic, polycarbonate, polyester, and the like.

  On the other hand, when the curable composition of the present invention contains a thermal cationic polymerization initiator, it can be cured by heating the curable composition, and the member and the member are bonded by this curing. I can do it. Therefore, the member to be bonded is preferably composed of a material having a material that can withstand heating (hereinafter referred to as “heat-resistant material”). Examples of such heat resistant materials include heat resistant glass, heat resistant resins such as phenol novolac epoxy resin and cresol novolac epoxy resin, but are not limited thereto.

  Here, since the hardened | cured material of the curable composition of this invention is excellent in a softness | flexibility and adhesiveness as mentioned above, even if shrinkage stress increases, it can maintain favorable adhesive force. Therefore, good adhesiveness can be realized even if the bonding interface between the members is an uneven shape.

  “The adhesive interface has an uneven shape” means that the adhesive interface is not flat but has undulations. When there is a depression and / or protrusion on the bonding surface of at least one member of the two or more members to be bonded, the bonding interface between the members can be formed into an uneven shape. The shape of the said dent and protrusion is not specifically limited, It may be comprised only by the plane, may be comprised only by the curved surface, and may be comprised by the plane and the curved surface.

  Examples of the member having a depression and / or protrusion on the adhesive surface include a lens, an optical waveguide, a fiber array, and a collimator lens array. Examples of the optical device including such a member include, but are not limited to, a fiber array, a WDM module, a collimator array, an optical modulator, an optical amplifier, a camera, a microscope, and a telescope.

  Hereinafter, an example of the optical device of the present invention will be described with reference to FIGS. However, the optical device of the present invention is not necessarily limited to the form described in FIGS.

  FIG. 1 is a schematic diagram showing an embodiment of a fiber array. FIG. 1 (a) is a schematic view of a fiber array 10 before bonding using the curable composition of the present invention, and FIG. 1 (b) is a diagram after bonding using the curable composition of the present invention. 1 is a schematic diagram of a fiber array 10. FIG.

As shown in FIG. 1A, the fiber array 10 includes a pressing groove substrate 11 having a flat surface and a V-groove substrate 12 having ribbon fibers 13. The ribbon fiber 13 is formed of one or more optical fibers. One or more V-shaped grooves are formed on the surface of the V-groove substrate 12, and a ribbon fiber 13 is disposed in these grooves. Therefore, a recess and a protrusion are formed on the surface of the V-groove substrate 12 on which the ribbon fiber 13 is disposed. As shown in FIG. 1B, in the fiber array 10, the surface of the pressing substrate 11 and the above-described surface The surface on which the ribbon fiber 13 of the V-groove substrate 12 is disposed is bonded using the curable composition 14 of the present invention. In this embodiment, the groove of the V-groove substrate is V-shaped, but the shape of the groove is not particularly limited, and for example, a U-shape or the like can be used.

  FIG. 2 is a schematic diagram showing an embodiment of a WDM module. FIG. 2 (a) is a schematic diagram of the WDW module 20 before bonding using the curable composition of the present invention, and FIG. 2 (b) is after bonding using the curable composition of the present invention. 1 is a schematic diagram of a WDW module 20.

  As shown in FIG. 2A, the WDM module 20 includes a first fiber array 21, an optical waveguide 25, and a second fiber array 22. The first fiber array 21 is provided with one optical fiber 23 so as to penetrate the substrate of the fiber array 21. Furthermore, one surface through which the optical fiber 23 passes is inclined with respect to the vertical direction. The second fiber array 22 is the same as the first fiber array except that two optical fibers 23 are provided so as to penetrate the substrate of the fiber array 22.

  The optical waveguide 25 is provided with two optical fibers 23 so as to pass through the substrate of the optical waveguide 25. Further, the two optical fibers 23 converge on one side of the substrate. Yes. That is, the substrate of the optical waveguide 25 has a surface on which one optical fiber is formed (hereinafter referred to as “surface 1”) and a surface on which two optical fibers are formed (hereinafter referred to as “surface 2”). Is written). A filter 26 is formed on the surface 1 so as to include the optical fiber 23. Further, the surface 1 and the surface 2 are inclined with respect to the vertical method so that the WDM module 20 is square when bonded to the first fiber array 21 and the second fiber array 22.

  In the WDM module 20, depressions and protrusions are formed on the respective surfaces through which the first fiber array 21, the second fiber array 22, and the optical fiber 23 of the optical waveguide 25 pass.

  As shown in FIG. 2B, in the WDM module 20, the inclined surface of the first fiber array 21 and the surface 1 of the optical waveguide 25 are connected to the inclined surface of the second fiber array 22 and the optical waveguide 25. The surface 2 is bonded using the curable composition 14 of the present invention.

  FIG. 3 is a schematic diagram showing an embodiment of a collimator array. FIG. 3 (a) is a schematic view of the collimator array 30 before bonding using the curable composition 14 of the present invention, and FIG. 3 (b) is after bonding using the curable composition 14 of the present invention. FIG. 3C and FIG. 3D are cross-sectional views of the collimator array 30.

  As shown in FIGS. 3A and 3C, the collimator array 30 includes a collimator lens array 35 and the fiber array 10. A plurality of lenses 36 are formed on the collimator lens array 35 so as to correspond one-to-one with the ribbon fibers 13 provided in the fiber array 10 when bonded to the fiber array 10. Examples of the lens 36 include glass, plastic, and a flat lens. On the surface of the collimator lens array 35 where the lens 36 is formed and the surface of the fiber array 10 where the ribbon fiber 13 is provided, depressions and protrusions are formed.

  As shown in FIGS. 3B and 3D, in the collimator array 30, the lenses 36 formed on the collimator lens array 35 and the ribbon fibers 13 formed on the fiber array 10 are in a one-to-one correspondence. The surface of the collimator lens array 35 on which the lens 36 is formed and the surface of the fiber array 10 on which the ribbon fiber 13 is provided are bonded using the curable composition 14 of the present invention.

<Optical device manufacturing method>
The method for producing an optical device of the present invention includes an application step of applying the curable composition of the present invention to a member, and an adhesion step of bringing at least one member into close contact with the portion where the curable composition of the member is applied. And the adhesion process which adhere | attaches members by hardening the said curable composition should just be included, and the conventionally well-known method for manufacturing an optical device can be used for another process.

  In the coating step, the member described in the above <Optical device> can be used as a member to which the curable composition of the present invention is applied. Moreover, the method of apply | coating the curable composition of this invention to the said member is not specifically limited, For example, the method of using a spray, immersion, a spin coat, a roll coater, etc. can be used. The curable composition of the present invention may be applied to one or more members.

  Further, the coating amount of the curable composition is not particularly limited as long as it is an amount capable of bonding the member to each other. For example, the curable composition layer generated by coating is preferably 0.1 μm to 1000 μm. More preferably, the coating amount may be adjusted so as to be 1 μm to 500 μm, more preferably 5 μm to 100 μm. In order to obtain such a curable composition layer, the viscosity of the curable composition at 25 ° C. is preferably adjusted to 10 to 2000 mPa · s, more preferably 30 to 1500 mPa · s, and further preferably 50 to 1000 mPa · s. do it.

  In the adhesion step, the member to be adhered may be such that the curable composition is applied to at least one member of the curable composition. That is, one or more members not coated with the curable composition may be adhered to one or more members coated with the curable composition, or the curable composition is coated. One or more members coated with the curable composition may be adhered to one or more members. Moreover, it does not specifically limit as a method of closely_contact | adhering members, For example, the method of closely_contact | adhering by fixing one member and making the other member contact is mentioned.

  In the bonding step, when the curable composition of the present invention contains a cationic photopolymerization initiator, the curable composition can be cured by irradiating the curable composition with light through the member. The members can be bonded together. Therefore, it is preferable that at least one of the members is the light transmissive member described above.

  As said light, although an ultraviolet-ray, visible light, X-ray | X_line, an electron beam etc. can be used, for example, it is preferable to use an ultraviolet-ray. Since ultraviolet rays have high energy, the curing reaction can be accelerated by irradiating the curable composition with ultraviolet rays, the curing rate of the curable composition can be increased, and the unreacted curable composition in the cured product. The amount of objects can be reduced.

  The method for irradiating the curable composition with visible light is not particularly limited, and examples thereof include a method using an incandescent bulb, a fluorescent lamp, and the like. The method of irradiating the curable composition with ultraviolet rays is not particularly limited, and examples thereof include a method using a low-pressure or high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like. When ultraviolet rays are used, the wavelength range is not particularly limited, but is preferably 150 nm to 400 nm, more preferably 200 nm to 380 nm.

  Since the curing state of the curable composition can be measured using a Fourier transform infrared spectrophotometer or a photochemical reaction calorimeter, the curing conditions for completely curing the cured product (light irradiation time, light intensity, etc.) Can be selected as appropriate.

  On the other hand, when the curable composition of the present invention contains a thermal cationic polymerization initiator, it can be cured by heating the curable composition, and the members can be bonded together by this curing. . Therefore, the member is preferably a member provided with the heat-resistant material described above. This can prevent the member from being deformed by heating. The method for heating the curable composition is not particularly limited, and a conventionally known heating method such as a heater can be used.

  Since the curing state of the curable composition can be measured using a Fourier transform infrared spectrometer or a photochemical reaction calorimeter, the curing conditions (heating temperature, heating time, etc.) for completely curing the cured product are appropriately determined. Can be selected.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  The following examples further illustrate the present invention in detail, but the present invention is not limited thereto.

[Example 1]
<Preparation of curable composition>
Each component was mixed in the ratio shown in the following Table 1, and the curable composition was manufactured.

  Also, Epicron TSR-960 (manufactured by Dainippon Ink & Chemicals, Inc.) as a carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound, jERYX-8000 (manufactured by Japan Epoxy Resin Co., Ltd.) as a hydrogenated bisphenol A type epoxy, fat Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.) as a cyclic epoxy compound, OXT-211 (manufactured by Toagosei Co., Ltd.) as an oxetane compound, and KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent As a onium salt, triphenylsulfonium hexafluorophosphate 50% propylene carbonate solution (manufactured by Sun Apro Co., Ltd .; CPI-100P) was used.

<Measurement of refractive index>
A 100 μm silicone rubber mold with 15 mm × 30 mm holes was placed on a 50 μm PET film, and the curable composition was poured into the silicone rubber mold. Thereafter, UV irradiation was performed for 400 s at 20 mW / cm ² using a high-pressure mercury lamp with a 50 μm PET film placed on the curable composition layer. After UV irradiation, a cured product of 100 μm was obtained by removing the two PET films and the silicone rubber mold. After leaving at room temperature for 24 hours, baking was performed at 100 ° C. for 2 hours. As a result, a sample for measuring the refractive index was obtained. The measurement sample was measured for refractive index at 25 ° C. and 589 nm using an Abbe refractometer NAR-1T manufactured by Atago Co., Ltd. The measurement results are shown in Table 1.

<Measurement of light transmittance>
A 100 μm silicon rubber mold with holes of 15 mm × 15 mm was placed on a 50 μm PET film, and the curable composition was poured into the silicon rubber mold. Thereafter, UV irradiation was performed for 400 s at 20 mW / cm ² using a high-pressure mercury lamp with a 50 μm PET film placed on the curable composition layer. After UV irradiation, a cured product of 100 μm was obtained by removing the two PET films and the silicone rubber mold. After leaving at room temperature for 24 hours, baking was performed at 100 ° C. for 2 hours. As a result, a sample for measuring the refractive index was obtained. The light transmittance of a wavelength region of 1200 nm or more and 1700 nm or less of this measurement sample was measured using an infrared spectrometer MAGNA-IR 750 manufactured by Nicorey. The measurement results are shown in Table 1.

<Measurement of peel strength and Young's modulus>
(How to create a sample)
0.05 g of the curable composition was applied onto borosilicate glass, and a slide glass on which a release agent had been applied in advance was placed through a 60 μm thickness gauge so that the release agent was in contact with the resin. Thereafter, UV irradiation was performed at 20 mW / cm ² for 400 s using a high pressure mercury lamp, and then the slide glass was removed to obtain a resin composition having a film thickness of 60 μm adhered on the borosilicate glass. After standing at room temperature for 3 hours, baking was performed at 100 ° C. for 2 hours. Thereafter, it was left at room temperature for 24 hours. As a result, a measurement sample before the high temperature and high humidity test was obtained. The peel strength and Young's modulus before the high temperature and high humidity test were measured using this sample.

(High temperature and high humidity environment test)
The sample obtained by the above preparation method was kept in an environment of 121 ° C. and humidity of 100 RH for 30 hours, and then left at room temperature for 24 hours. As a result, a sample after the high temperature and high humidity environment test was obtained.

(Peel strength test)
Using a BN cutting blade, the cutting blade was moved in a constant speed mode at a horizontal speed of 1 μm / s with a SAICAS manufactured by Daipura Wintes Co., Ltd. for the samples before and after the high temperature and high humidity environment test. The horizontal force received by the cutting edge per blade width at this time was defined as peel strength (kN / m). The peel strength before and after the high temperature and high humidity environment test is shown in Table 2.

(Young's modulus test)
The samples before and after the high-temperature and high-humidity environment test were subjected to penetration and withdrawal at a speed of 1 mN / s in a load increasing mode using a Vickers indenter with a WIN-HCU manufactured by Fisher Instruments Co., Ltd. In this way, the Young's modulus of the sample before and after the high temperature and high humidity environment test was measured. The Young's modulus change is shown in Table 3.

[Example 2]
<Preparation of curable composition>
EPB-13 (manufactured by Nippon Soda Co., Ltd.) is used as the epoxidized polybutadiene compound in place of the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound, and OXT-101 (Toagosei Co., Ltd.) is used as the oxetane compound having a hydroxyl group. A curable composition was prepared in the same manner as in Example 1 except that the product was added.

<Measurement of refractive index>
About the said curable composition, it carried out similarly to Example 1, and measured the refractive index of hardened | cured material. The results are shown in Table 1.

<Measurement of light transmittance>
About the said curable composition, it carried out similarly to Example 1, and measured the light transmittance of hardened | cured material. The results are shown in Table 1.

<Measurement of peel strength and Young's modulus>
About the said curable composition, it carried out similarly to Example 1, and measured the peeling strength and Young's modulus of hardened | cured material. The results are shown in Tables 2 and 3, respectively.

Example 3
<Preparation of curable composition>
A curable composition was prepared in the same manner as in Example 1 except that OXT-101 (manufactured by Toagosei Co., Ltd.) was added as an oxetane compound having a hydroxyl group.

<Measurement of refractive index>
About the said curable composition, it carried out similarly to Example 1, and measured the refractive index of hardened | cured material. The results are shown in Table 1.

<Measurement of light transmittance>
About the said curable composition, it carried out similarly to Example 1, and measured the light transmittance of hardened | cured material. The results are shown in Table 1.

<Measurement of peel strength and Young's modulus>
About the said curable composition, it carried out similarly to Example 1, and measured the peeling strength and Young's modulus of hardened | cured material. The results are shown in Tables 2 and 3, respectively.

Example 4
<Preparation of curable composition>
As an oxonium salt not dissolved in a high boiling point solvent, an oxonium salt dissolved in a high boiling point solvent instead of a 50% propylene carbonate solution of triphenylonium hexafluorophosphate (manufactured by Sun Apro Co., Ltd .; CPI-100P) A curable composition was prepared in the same manner as in Example 3 except that triphenylonium hexafluorophosphate (manufactured by San Apro Co., Ltd .; CPI-110P) was used.

<Measurement of refractive index>
About the said curable composition, it carried out similarly to Example 1, and measured the refractive index of hardened | cured material. The results are shown in Table 1.

<Measurement of light transmittance>
About the said curable composition, it carried out similarly to Example 1, and measured the light transmittance of hardened | cured material. The results are shown in Table 1.

<Measurement of peel strength and Young's modulus>
About the said curable composition, it carried out similarly to Example 1, and measured the peeling strength and Young's modulus of hardened | cured material. The results are shown in Tables 2 and 3, respectively.

[Comparative Example 1]
<Preparation of curable composition>
A curable composition was prepared in the same manner as in Example 1 except that the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound was not used.

<Measurement of refractive index>
About the said curable composition, it carried out similarly to Example 1, and measured the refractive index of hardened | cured material. The results are shown in Table 1.

<Measurement of light transmittance>
About the said curable composition, it carried out similarly to Example 1, and measured the light transmittance of hardened | cured material. The results are shown in Table 1.

<Measurement of peel strength and Young's modulus>
About the said curable composition, it carried out similarly to Example 1, and measured the peeling strength and Young's modulus of hardened | cured material. The results are shown in Tables 2 and 3, respectively.

  Table 1 shows the ratio of each component of the constituent compounds of the curable compositions of Examples 1 to 4 and Comparative Example 1 in parts by weight. Moreover, the refractive index of the light of wavelength 589nm and the light transmittance of wavelength 1200-1700nm in 25 degreeC of the hardened | cured material of Examples 1-4 and the comparative example 1 are shown.

  Table 2 shows the peel strengths of Examples 1 to 4 and Comparative Example 1 before and after the high temperature and high humidity environment test.

  In Table 2, by comparing the curable compositions of Examples 1 to 4 and the curable composition of Comparative Example 1, carboxy-terminated butadiene nitrile rubber modified bisphenol A type epoxy and / or epoxidized polybutadiene are contained. This shows that the change in peel strength after the high-temperature and high-humidity test is small. Moreover, by comparing the curable compositions of Examples 3 and 4, it can be seen that the change in peel strength after high temperature and high humidity is further reduced by the absence of propylene carbonate, which is a high boiling point solvent.

  Table 3 shows the Young's modulus of Examples 1 to 4 and Comparative Example 1 before and after the high temperature and high humidity environment test.

  In Table 3, by comparing Examples 1 to 4 and Comparative Example 1, the presence of carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy and / or epoxidized polybutadiene allows Young before the high temperature and high humidity environment test. It can be seen that the rate is lower than that of Comparative Example 1 and flexibility is imparted. In addition, when considered together with the previous peel strength test results, Examples 1 to 4 were imparted with flexibility, so that the decrease in peel strength after the high temperature and high humidity test was reduced, and the peel resistance was improved. I understand.

  Further, by comparing the curable compositions of Examples 3 and 4, Example 4 has a smaller increase in Young's modulus after the high-temperature and high-humidity environment test than Example 3, and the high-temperature and high-humidity environment test is in progress. It can be seen that the extra curing reaction that occurs in is small. When considered together with the previous peel strength test results, Example 4 shows that the extra curing reaction that occurs during the high-temperature and high-humidity environment test is small, whereby the change in peel strength is small.

  The cured product of the curable composition of the present invention does not deteriorate or peel off even at high temperature or high temperature and high humidity. Therefore, the curable composition of the present invention can be suitably used as an adhesive, a paint, a coating agent, a sealing agent, and a sealing agent for display devices such as optical devices and liquid crystals. Therefore, the present invention can be used in the optical device manufacturing industry such as an optical multiplexer / demultiplexer, a collimator, an optical modulator, an optical amplifier, a camera, a microscope, and a telescope used for WDM (optical wavelength division multiplexing).

(A) is a schematic diagram of the fiber array before bonding using the curable composition of the present invention, (b) is a schematic diagram of the fiber array after bonding using the curable composition of the present invention. It is. (A) is a schematic diagram of the WDW module before bonding using the curable composition of the present invention, and (b) is a schematic diagram of the WDW module after bonding using the curable composition of the present invention. It is. (A) is a schematic diagram of the collimator array before bonding using the curable composition of the present invention, (b) is a schematic diagram of the collimator array after bonding using the curable composition of the present invention. (C) and (d) are cross-sectional views of the collimator array.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Fiber array 11 Holding substrate 12 V groove board 13 Ribbon fiber 14 Curable composition 20 WDW module 21 1st fiber array 22 2nd fiber array 23 Optical fiber 25 Optical waveguide 26 Filter 30 Collimator array 35 Collimator lens array 36 Lens

Claims (10)

A carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound (A-1) and / or an epoxidized polybutadiene compound (A-2);
A curable composition containing a cationically polymerizable compound (B) other than the above (A-1) and (A-2),
The cationic polymerizable compound (B) is an oxetane compound having an alicyclic epoxy compound and a hydroxyl group,
The curable composition was irradiated with ultraviolet rays at 20 mW / cm ² for 400 s using a high-pressure mercury lamp to obtain a cured product having a thickness of 100 μm. The obtained cured product was allowed to stand at room temperature for 24 hours, and then 100 ° C. A curable composition having a refractive index of 1.40 or more and 1.60 or less at 25 ° C. and 589 nm of a cured product cured under conditions of baking for 2 hours . The carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound (A-1) and / or the epoxidized polybutadiene compound (A-2) does not contain a solvent having a boiling point of 180 ° C. or higher. Item 2. The curable composition according to Item 1. The curable composition according to claim 1 or 2, characterized in that further contains a cationic polymerization initiator. 4. The curable composition according to claim 3 , wherein the cationic polymerization initiator is an onium salt-based photocationic polymerization initiator. The curable composition according to claim 4 , wherein the onium salt photocationic polymerization initiator is not dissolved in a solvent having a boiling point of 180 ° C. or higher . The curable composition according to any one of claims 1 to 5, characterized in that further contains a silane coupling agent. A thickness of 100μm of the cured product of the curable composition, the light transmittance in the following 1200nm or 1700nm of the cured product, claim 1-6, characterized in that 100% or less 60% The curable composition according to item 1. An optical device manufactured using the curable composition according to any one of claims 1 to 7 . The optical device according to claim 8 , wherein the optical device has two or more members. The optical device according to claim 8 or 9 material used for the member, characterized in that an organic material or synthetic quartz.

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