JP2008308589A - Curable composition and optical device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a curable composition that realizes adhesion of optical device for a long period of time without causing bad conditions such as formation of a salt with an alkali metal, metal corrosion, release etc., even in a high-temperature environment or a high-temperature and high-humidity environment and to provide an optical device using the same. <P>SOLUTION: The curable composition comprises a cationically polymerizable compound and a cationic polymerization initiator represented by general formula (1). The cured product of the curable composition has a change in Young's modulus between before and after retention at 121°C or 121°C at 100 RH% for 48 hours of ≥1.0 and ≤1.5. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable composition and an optical device using the same, and specifically includes a polymerization initiator excellent in cationic polymerizability, and exhibits a shrinkage stress in a high temperature environment or a high temperature and high humidity environment. The present invention relates to a curable composition with little increase and less salt formation with an alkali metal, 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. The ultraviolet curable adhesive includes a radical type and a cationic type. Radical ultraviolet curable adhesives have the advantage of high reactivity and excellent fast curing and fixing properties, but are not suitable for bonding uneven portions where ultraviolet rays are difficult to reach. On the other hand, cationic ultraviolet curable adhesives are inferior to radical ultraviolet curable adhesives in terms of reactivity, but they can be cured even in areas where ultraviolet rays do not reach by using thermosetting together. ing.

Here, conventional cationic UV curable adhesives include a cationic polymerization initiator as a reaction initiator, and generally onium salt polymerization initiators such as iodonium salts and sulfonium salts are used. It has been. In particular, sulfonium salt polymerization initiators represented by triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, and triphenylsulfonium hexafluoroantimonate are relatively concerned about storage stability and metal corrosion due to outgassing. Since it is few, it is used favorably (refer 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)

The anion portion of the sulfonium salt polymerization initiator represented by the above-mentioned triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, and triphenylsulfonium hexafluoroantimonate is BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ^−. Therefore, the cationic polymerization activity is not sufficient, and the curing reaction gradually proceeds after UV curing. Therefore, the curing of the unreacted cationic polymerizable compound is promoted over a wide range, which causes an increase in the shrinkage stress of the cured product due to the curing reaction. Accordingly, there arises a problem that a problem such as peeling of the cured product occurs.

  Further, in the glass member containing an alkali metal such as sodium or potassium, the sulfonium salt polymerization initiator and the alkali metal form a salt. As a result, opaque foreign matters are generated in the cured product, causing problems such as peeling of the cured product and deterioration of the light transmittance of the cured product.

  The present invention has been made in view of the above problems, and its purpose is to form a salt with an alkali metal, corrode metal, and exfoliation even in a high temperature environment or a high temperature and high humidity environment. An object of the present invention is to provide a curable composition that can realize adhesion of an optical device over a long period of time without causing such problems as above, and an optical device using the same.

  As a result of intensive research in view of the above problems, the present inventor has improved the cationic polymerizability in ultraviolet curing by making the anion portion of the cationic polymerization initiator highly water repellent and / or increasing the molecular weight of the anion portion. The present inventors have found that cationic polymerization is reduced under a high temperature environment or a high temperature and high humidity environment, and have completed the present invention.

  That is, the curable composition of the present invention is a curable composition containing a cationically polymerizable compound and a cationic polymerization initiator represented by the general formula (1) in order to solve the above-described problem, The change in Young's modulus before and after holding the cured product of the adhesive composition at 121 ° C. or 121 ° C. and 100 RH% for 48 hours is 1.0 or more and 1.5 or less.

(In formula (1), R _{1 to} R ₃ each independently represents an aryl group, a heterocyclic group, or an alkyl group. Rf represents an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms. X, m, and n are integers of m = 6 and n = 1 to 5 when X is P, m = 6 when X is Sb, integers of n = 1 to 5, and m = when X is B 4, n is an integer of 1 to 3.)
According to the above invention, since the cationic polymerization initiator has an alkyl group represented by Rf, the molecular weight of the anion portion is increased. Thereby, since the cationic polymerization activity by ultraviolet curing becomes high, cationic polymerization under a high temperature environment or a high temperature and high humidity environment can be reduced.

Furthermore, since R _{1 to} R ₃ and Rf are all hydrophobic groups having a carbon skeleton, the water repellency of the cationic polymerization initiator is increased. Therefore, the acid generated from the cationic polymerization initiator can be prevented from diffusing through the water molecule. Thus, by improving the molecular weight of the anion moiety and imparting water repellency by the alkyl group, the reactivity by ultraviolet curing is improved, and cationic polymerization in a high temperature environment or a high temperature and high humidity environment is reduced.

  Therefore, when the cured product of the curable composition is placed in the above environment, the acid generated from the cationic polymerization initiator diffuses into the cured product and the uncured cationic polymerizable compound is cured. Can be prevented. As a result, it is possible to prevent the shrinkage stress of the cured product from increasing and foreign matter from being generated in the above environment. Therefore, when the cured product and the adherend are bonded, the adhesive strength of the cured product to the adherend Can be prevented from being lowered or peeled off from the adherend. In other words, the cured product of the curable composition has the adhesiveness excellent in heat resistance and water resistance to the adherend because the cationic polymerization initiator is used.

  Further, since the water repellency of the cationic polymerization initiator is increased, salt formation between the cationic polymerization initiator and the alkali metal mediated by water molecules can be prevented. For this reason, in the hardened | cured material of the curable composition containing the said cationic polymerization initiator, it can prevent that an opaque foreign material arises between the to-be-adhered body containing an alkali metal, and the said hardened | cured material. . As a result, it is possible to prevent the cured product from being peeled off from the adherend and the light transmission between the cured product and the adherend being deteriorated.

  Moreover, since Young's modulus means an elastic modulus, as the Young's modulus change comparing the Young's modulus before holding the cured product in a high-temperature environment or a high-temperature and high-humidity environment with the subsequent Young's modulus is closer to 1, This indicates that the cured product after being held in a high temperature environment or a high temperature and high humidity environment is not cured. In other words, the cured product having a change in Young's modulus close to 1 is hard to be cured, so that it can be said that the increase in shrinkage stress is small. The cured product of the curable composition of the present invention has excellent flexibility because the Young's modulus change before and after being held at 121 ° C or 121 ° C and 100RH% for 48 hours is 1.0 or more and 1.5 or less. .

  In the curable composition of the present invention, the cationically polymerizable compound is preferably one or more compounds selected from the group consisting of epoxy compounds, oxetane compounds and vinyl ether compounds.

  Moreover, in the curable composition of this invention, it is preferable that the said cationically polymerizable compound contains an epoxy compound and an oxetane compound. Thereby, since hardening occurs cooperatively between an epoxy compound and an oxetane compound, hardening of a curable composition can be accelerated | stimulated. 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.

  In the curable composition of the present invention, the epoxy compound is composed of an alicyclic epoxy compound, an epoxy compound having a polybutadiene structure, a carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound, and an epoxidized polybutadiene compound. One or more selected compounds are preferred.

  Since the said alicyclic epoxy compound is excellent in sclerosis | hardenability, hardening of a curable composition can be accelerated | stimulated. As a result, since the amount of the uncured product existing 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. Moreover, since the epoxy compound which has the said polybutadiene structure has flexibility, the softness | flexibility of hardened | cured material can be improved by using this compound.

  Further, the epoxidized polybutadiene compound is excellent in curability. Furthermore, the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound is excellent in adhesion and flexibility, and the epoxidized polybutadiene compound is excellent in flexibility. Therefore, the softness | flexibility and adhesiveness of hardened | cured material can be improved with these compounds. Therefore, by curing a curable composition containing these compounds, it is possible to provide a cured product with few uncured products and excellent adhesiveness.

  Moreover, in the curable composition of this invention, it is preferable that the said oxetane compound has a hydroxyl group. According to this, hardening of an epoxy compound can be accelerated | stimulated with the said hydroxyl group. As a result, since the amount of the uncured product existing 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.

  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, 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. Furthermore, in the hardened | cured material of a curable composition, it can prevent that an opaque foreign material arises between the to-be-adhered body containing an alkali metal, and the said hardened | cured material. Therefore, even if the optical device contains an alkali metal, it is possible to prevent the light transmittance of the optical device from deteriorating.

  And since the said curable composition is used for the said optical device, the said optical device can implement | achieve the outstanding heat resistance, moisture resistance, and light transmittance.

  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. Furthermore, in the hardened | cured material of a curable composition, it can prevent that an opaque foreign material arises between the to-be-adhered body containing an alkali metal, and the said hardened | cured material. Therefore, it is possible to prevent the members from being separated from each other and the light transmittance of the members from being deteriorated in a high temperature environment or a high temperature and high humidity environment. Therefore, the optical device can realize excellent heat resistance, moisture resistance, and light transmittance.

  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 is a curable composition containing the cationic polymerization initiator represented by the general formula (1) and the cationic polymerizable compound, and curing of the curable composition. The Young's modulus change before and after holding the product at 121 ° C. or 121 ° C. and 100 RH% for 48 hours is 1.0 or more and 1.5 or less. According to the above invention, since the cationic polymerization initiator has an alkyl group represented by Rf, the molecular weight of the anion portion is increased. Thereby, since the cationic polymerization activity by ultraviolet rays increases, the cationic polymerization under a high temperature environment or a high temperature and high humidity environment can be reduced.

Furthermore, since R _{1 to} R ₃ and Rf are all hydrophobic groups having a carbon skeleton, the water repellency of the cationic polymerization initiator is increased. Therefore, the acid generated from the cationic polymerization initiator can be prevented from diffusing through the water molecule. Thus, cationic polymerization in a high temperature environment or a high temperature and high humidity environment is reduced by improving the molecular weight of the anion moiety and imparting water repellency by an alkyl group.

  Therefore, when the cured product of the curable composition is placed in the above environment, the acid generated from the cationic polymerization initiator diffuses into the cured product and the uncured cationic polymerizable compound is cured. Can be prevented. As a result, it is possible to prevent an increase in the shrinkage stress of the cured product in the above environment. Therefore, when the cured product and the adherend are bonded, a decrease in the adhesive force of the cured product to the adherend or the adherend. There is an effect that peeling from the body can be prevented. In other words, the cured product of the curable composition has the adhesiveness excellent in heat resistance and water resistance to the adherend because the cationic polymerization initiator is used.

  In addition, the cationic polymerization initiator becomes hydrophobic, and the acid generated from the cationic polymerization initiator is prevented from diffusing through water molecules, so that the cationic polymerization initiator forms a salt with an alkali metal. Can be prevented. For this reason, in the hardened | cured material of the curable composition containing the said cationic polymerization initiator, it can prevent that an opaque foreign material arises between the to-be-adhered body containing an alkali metal, and the said hardened | cured material. . Thereby, there exists an effect that it can prevent peeling of the hardened | cured material from the said to-be-adhered body, and deterioration of the light transmittance in hardened | cured material and the said to-be-adhered body.

  Moreover, since Young's modulus means an elastic modulus, as the Young's modulus change comparing the Young's modulus before holding the cured product in a high-temperature environment or a high-temperature and high-humidity environment with the subsequent Young's modulus is closer to 1, This indicates that the cured product after being held in a high temperature environment or a high temperature and high humidity environment is not cured. In other words, the cured product having a change in Young's modulus close to 1 is hard to be cured, so that it can be said that the increase in shrinkage stress is small. The cured product of the curable composition of the present invention has a change in Young's modulus before and after being held at 121 ° C. or 121 ° C. and 100 RH% for 48 hours, being 1.0 or more and 1.5 or less. Play.

  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. Furthermore, in the hardened | cured material of a curable composition, it can prevent that an opaque foreign material arises between the to-be-adhered body containing an alkali metal, and the said hardened | cured material. Therefore, even when an alkali metal is contained in the optical device, it is possible to prevent the light transmittance of the optical device from being deteriorated by using the curable composition.

  And since the said curable composition is used for the said optical device, the said optical device has the effect that the outstanding heat resistance, moisture resistance, and light transmittance can be implement | achieved.

[1: Curable composition]
<Curable composition>
The curable composition of the present invention contains a cationic polymerization initiator represented by general formula (1) and a cationic polymerizable compound, and the cured product of the curable composition is 121 ° C. or 121 ° C. and 100 RH% for 48 hours. The Young's modulus change before and after holding is preferably 1.0 or more and 1.5 or less, more preferably 1.05 or more and 1.45 or less, and further preferably 1.10 or more and 1.40 or less.

(In formula (1), R _{1 to} R ₃ each independently represents an aryl group, a heterocyclic group, or an alkyl group. Rf represents an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms. X, m, and n are integers of m = 6 and n = 1 to 5 when X is P, m = 6 when X is Sb, integers of n = 1 to 5, and m = when X is B 4, n is an integer of 1 to 3.)
In this specification, “under a high temperature environment” means an environment having a temperature of 121 ° C. or higher, and “under a high temperature and high humidity environment” means a temperature of 121 ° C. or higher and a humidity of preferably 100 RH. % Environment. “Holding the cured product in a high temperature environment or a high temperature and high humidity environment” means that the cured product is preferably exposed to the above-described high temperature environment or high temperature and high humidity environment for 48 hours or more.

  In the present specification, the “cured product of the curable composition” refers to a product obtained by curing a cationically polymerizable compound. Since the cationic polymerization initiator represented by the general formula (1) is contained in the curable composition, the cationic polymerizable compound can be efficiently cured by activating the cationic polymerization initiator. Thereby, the hardened | cured material of a curable composition can be obtained. However, the method for obtaining a cured product of the curable composition is not limited thereto.

  In addition, the method for activating the cationic polymerization initiator is not particularly limited. For example, the light that can be activated by irradiating the cationic polymerization initiator with light or heating can be exemplified by ultraviolet rays. Visible light, X-rays, electron beams, and the like can be used, but it is preferable to use ultraviolet rays. 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. Moreover, it does not specifically limit as a method of irradiating a curable composition with an ultraviolet-ray, For example, the method of using a low pressure or a high pressure mercury lamp, a metal halide lamp, a xenon lamp etc. is mentioned. When ultraviolet rays are used, the wavelength range is not particularly limited, but is preferably 150 nm to 400 nm, and more preferably 200 nm to 380 nm.

  Moreover, it does not specifically limit as a method of heating a curable composition, Conventionally well-known heating methods, such as a heater, can be used.

  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 (light irradiation time, light light) for completely curing the cured product Strength, heating temperature, heating time, etc.) can be appropriately selected.

  The change in Young's modulus before and after holding the cured product of the curable composition in a high-temperature environment or a high-temperature and high-humidity environment is the same as after changing the cured product of the curable composition in a high-temperature environment or a high-temperature and high-humidity environment. It can be determined by dividing the Young's modulus of the cured product by the Young's modulus of the previous cured product.

  Here, since the Young's modulus means an elastic modulus, the closer the Young's modulus change to 1, the more the cured product after being held in a high temperature environment or a high temperature and high humidity environment is not cured. Yes. In other words, the cured product having a change in Young's modulus close to 1 is hard to be cured, so that it can be said that the increase in shrinkage stress is small. The cured product of the curable composition of the present invention has a Young's modulus change before and after being held at 121 ° C. or 121 ° C. and 100 RH% for 48 hours, preferably 1.0 or more and 1.5 or less, more preferably 1.05 or more and 1 .45 or less, more preferably 1.10 or more and 1.40 or less.

  The method for obtaining the Young's modulus is not particularly limited, and a conventionally known method can be used. For example, in the following examples, by using a WIN-HCU manufactured by Fischer Instruments Co., Ltd., with a Vickers indenter, in a load increasing mode, and performing penetration and withdrawal at a speed of 1 mN / s on the cured product. The stress of the cured product is examined. And the Young's modulus of hardened | cured material is calculated | required from this stress.

  First, the cationic polymerization initiator represented by the general formula (1) will be described. Since the cationic polymerization initiator represented by the general formula (1) promotes the curing of the cationic polymerizable compound, a cured product of the curable composition can be obtained efficiently.

The functional groups represented by R _{1 to} R ₃ in the above formula (1) are each independently an aryl group, a heterocyclic group, or an alkyl group.

Examples of the aryl group in R _{1 to} R ₃ include, but are not limited to, a phenyl group, a tolyl group, a biphenyl group, or a naphthyl group. Examples of the heterocyclic group in R _{1 to} R ₃ include a furyl group, a thienyl group, a thiazolyl group, a benzofuryl group, a benzothiophenyl group, a benzothiazolyl group, and a benzoxazolyl group. It is not limited.

Examples of the alkyl group in R _{1 to} R ₃ include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Further, the alkyl group may be linear or branched, and the carbon number thereof is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 8.

For example, the functional group represented by R _{1 to} R ₃ in the above formula (1) is preferably a linear or branched aryl group or an alkyl group. By using these functional groups, the cationic polymerization activity of the compound represented by the above formula (1) can be enhanced, and the water repellency can be enhanced most. Therefore, it is possible to provide a cationic polymerization initiator in which the shrinkage stress hardly increases in a high temperature environment or a high temperature and high humidity environment.

  Rf in the above formula (1) is an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms. Examples of the alkyl group in Rf include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. These alkyl groups may be linear or branched. The number of carbon atoms of the alkyl group is preferably in the range of 1 to 8, and more preferably in the range of 1 to 4.

  Specifically, the “alkyl group in which a part of hydrogen atoms are substituted with fluorine atoms” is preferably 80% or more, more preferably 90%, more preferably 95% or more of hydrogen atoms. It is a substituted alkyl group. Cationic polymerization initiators having these characteristics are highly active and can accelerate the curing of the curable composition. For this reason, Rf in the above formula (1) is preferably an alkyl group in which all hydrogen atoms are substituted with fluorine, that is, a perfluoroalkyl group.

  Rf in the formula (1) used in the present invention is particularly preferably a perfluoroalkyl group containing a linear or branched group having 1 to 8 carbon atoms. By making Rf a perfluoroalkyl group having a carbon number in the above range, a cationic polymerization initiator having excellent curability can be provided.

  In the above formula (1), when X is P, m = 6 and n = 2 to 4, and when X is Sb, m = 6 and n = 2 to 4 and X is B. In this case, it is preferable that m = 4, n = 2 or 3. If X, m, and n are the above numerical values, the balance between curability and hydrophobicity is good.

  The method for producing the cationic polymerization initiator represented by the general formula (1) is not particularly limited. For example, it can be produced by a reaction between an alkali metal salt of fluorinated alkylyl fluoro acid and an onium halide ion salt. .

  Examples of the cationic polymerization initiator represented by the general formula (1) include triphenylsulfonium phosphate (manufactured by San Apro: K-1S).

  The addition ratio of the cationic polymerization initiator represented by the general formula (1) in the curable composition is preferably 0.5 to 10 parts by weight, more preferably 1 to 100 parts by weight of the curable composition. Parts by weight to 5 parts by weight, more preferably 1.5 parts by weight to 3 parts by weight. By setting the addition ratio of the cationic polymerization initiator within the above range, curing can be performed so that a cured product with a small amount of uncured cationic polymerizable compound can be obtained. Furthermore, the curing of the uncured cationically polymerizable compound in a high temperature environment or a high temperature and high humidity environment can be reduced.

  Moreover, the curable composition of this invention may contain the cationic polymerization initiator represented by General formula (2).

(In Formula (2), R ₄ and R ₅ each independently represents an aryl group, a heterocyclic group, or an alkyl group. Rf represents an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms. N represents an integer of 1 to 5.)
In the formula (2), R ₄ , R ₅ , Rf and the addition ratio are the same as those described in the formula (1). Therefore, by having an alkyl group represented by Rf, the anion portion of the compound represented by the general formula (2) becomes a polymer. Therefore, since the activity of the cationic polymerization initiator can be increased, the cationic polymerization can be reduced under a high temperature environment or a high temperature and high humidity environment.

Further, since R _{4 to} R ₅ and Rf are all hydrophobic groups having a carbon skeleton, water repellency is increased. Therefore, it is possible to reduce the diffusion of the acid generated from the cationic polymerization initiator through the water molecule. Moreover, it is possible to prevent the formation of an alkali metal and a salt by improving the molecular weight and imparting water repellency by an alkyl group.

  Moreover, in the said Formula (2), it is preferable that it is an integer of n = 2-4. When n is the above numerical value, the balance between curability and hydrophobicity is good. Although the manufacturing method of the compound represented by the said General formula (2) is not specifically limited, For example, it can manufacture by reaction with the alkali metal salt of fluorinated alkylyl fluoro acid, and the halogen ion salt of onium.

  Next, the cationic polymerizable compound will be described. A cationically polymerizable compound is a compound whose curing is induced by a cationic polymerization initiator. Although it does not specifically limit as a cation polymeric compound which can be used for the curable composition of this invention, For example, an epoxy compound, an oxetane compound, a vinyl ether compound etc. are mentioned. These cationically polymerizable compounds can be used alone or in combination of two or more.

  The addition ratio of the epoxy compound 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. If the addition ratio of the epoxy compound is within the above range, the amount of the epoxy compound to be cured is appropriate, so that a cured product having a small amount of the uncured epoxy compound can be obtained.

  The addition ratio of the oxetane compound is preferably 10 parts by weight to 80 parts by weight, more preferably 20 parts by weight to 70 parts by weight, and further preferably 30 parts by weight to 60 parts by weight with respect to 100 parts by weight of the curable composition. It is. If the addition ratio of the oxetane compound is within the above range, the amount of the oxetane compound to be cured is appropriate, so that a cured product having a small amount of the uncured oxetane compound can be obtained.

  Furthermore, the addition ratio of the vinyl ether compound 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. Part. If the addition ratio of the vinyl ether compound is within the above range, the amount of the vinyl ether compound to be cured is appropriate, so that a cured product having a small amount of the uncured vinyl ether compound can be obtained.

  The epoxy compound is a general term for compounds having at least one epoxy group in the molecule. For example, an alicyclic epoxy compound, an epoxy compound having a polybutadiene structure, a carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound, Examples include, but are not limited to, epoxidized polybutadiene compounds and aromatic epoxy compounds. These epoxy compounds can be used alone or in combination of two or more.

  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 in which an epoxy bond is formed in the alicyclic structure. For example, 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-epoxycyclohexyl Examples include, but are not limited to, methyl-3 ′, 4′-epoxycyclohexanecarboxylate. These alicyclic epoxy compounds can be used alone or in combination of two or more.

  Since the said alicyclic epoxy compound is excellent in sclerosis | hardenability, hardening of a curable composition can be accelerated | stimulated. As a result, since the amount of the uncured product existing in the cured product can be reduced, it is possible to prevent foreign matters from being generated in a high temperature environment or a high temperature and high humidity environment.

  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 epoxy compound having a polybutadiene structure is a polymer of butadiene having at least one epoxy group, and examples thereof include addition reaction products of α, ω-polybutadiene dicarboxylic acid and bisphenol A type epoxy resin. It is not limited. These epoxy compounds having a polybutadiene structure can be used alone or in combination of two or more. Since the epoxy compound having the polybutadiene structure has flexibility, a cured product having excellent flexibility can be provided by curing a curable composition containing the compound.

  The method for producing the carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound is not particularly limited.

  The carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound has flexibility and adhesiveness. Therefore, by curing a curable composition containing this compound, a cured product having excellent flexibility and adhesiveness can be provided. Although the manufacturing method of the said epoxidized polybutadiene compound is not specifically limited, For example, it can manufacture by performing the oxidation reaction of polybutadiene.

  The epoxidized polybutadiene compound is excellent in curability. Furthermore, since there is flexibility, the flexibility of the cured product can be improved. Therefore, when the cured product of the curable composition containing this compound is placed in a high-temperature environment or a high-temperature and high-humidity environment, an increase in shrinkage stress accompanying further curing of the cured product can be reduced. It can prevent that the adhesive force with respect to the to-be-adhered body of the said hardened | cured material falls. In other words, a cured product excellent in heat resistance and moisture resistance in terms of adhesiveness can be provided.

  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), di [1-ethyl (3-oxetanyl)] methyl ether and the like, but are 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 because of good curability. Examples of such oxetane compounds include, but are not limited to, 2-hydroxymethyl oxetane, 3-methyl-3-oxetane methanol, and the like. These oxetane compounds can be used alone or in combination of two or more.

  Examples of the vinyl ether compound include ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane trivinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanediol. Examples thereof include, but are not limited to, monovinyl ether, 9-hydroxynonyl vinyl ether, and propylene glycol monovinyl ether. These vinyl ether compounds can be used alone or in combination of two or more.

  The above-mentioned epoxy compound, oxetane compound, and vinyl ether compound can be used alone or in combination of two or more. In particular, it is preferable to use an epoxy compound and an oxetane compound in combination. Thereby, since hardening occurs cooperatively between an epoxy compound and an oxetane compound, hardening of a curable composition can be accelerated | stimulated.

  It is more preferable to use an alicyclic epoxy compound and an oxetane compound having a hydroxyl group in combination. Thereby, since curing occurs more cooperatively between the alicyclic epoxy compound and the oxetane compound having a hydroxyl group, it is possible to further prevent foreign matters from being generated in a high temperature environment or a high temperature and high humidity environment.

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

(A) Activator of Cationic Polymerization Initiator The activity of the cationic polymerization initiator can be increased by using a cationic polymerization initiator activator. 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 cationic polymerization initiator activator include, but are not limited to, a sensitizer and the like.

  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 can be preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the curable composition.

(B) Silane coupling agent The silane coupling agent has a property of chemically bonding an inorganic material or a metal material to 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 parts by weight to 15 parts by weight, more preferably 1 part by weight to 10 parts by weight, and further preferably 3 parts by weight with respect to 100 parts by weight of the curable composition. 8 parts by weight.

(C) 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 heat resistance 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 20 to 70 parts by weight with respect to 100 parts by weight of the curable composition.

<Method for producing curable composition>
The curable composition of this invention can be manufactured by mixing using a conventionally well-known method, such as stirring a cationically polymerizable compound and a cationic polymerization initiator, for example. Furthermore, you may mix each component of said (a)-(c) as needed. Moreover, although the curable composition of this invention may be normally used as it is as a mixture of each said component, it may be melt | dissolved and used in an organic solvent. Thereby, the viscosity of a curable composition can be adjusted and the smoothness after application | coating can be ensured.

  Examples of the organic solvent that can be used include toluene, xylene, methyl ethyl ketone, isopropanol, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, and diethylene glycol monodiethyl ether. When an organic solvent is used, the amount used is appropriately determined according to the purpose.

  The hardened | cured material of the curable composition of this invention contains the cationic polymerization initiator containing the compound represented by General formula (1) or (2) as mentioned above. Since the cationic polymerization initiator represented by the general formula (1) or (2) has an alkyl group represented by Rf, the molecular weight of the anion portion is increased. As a result, the activity of the cationic polymerization is increased, so that the cationic polymerization under a high temperature environment or a high temperature and high humidity environment can be reduced.

Furthermore, since R _{1 to} R ₃ and Rf are all hydrophobic groups having a carbon skeleton, the water repellency of the cationic polymerization initiator is increased. Therefore, it is possible to reduce the diffusion of the acid generated from the cationic polymerization initiator through the water molecule. Thus, cationic polymerization in a high temperature environment or a high temperature and high humidity environment can be reduced by improving the molecular weight of the anion moiety and imparting water repellency by an alkyl group.

  Therefore, when the hardened | cured material of a curable composition is put in the said environment, it can prevent that an unhardened cationically polymerizable compound hardens | cures. As a result, it is possible to prevent an increase in the shrinkage stress of the cured product in the above environment. Therefore, when the cured product and the adherend are bonded, a decrease in the adhesive force of the cured product to the adherend or the adherend. Detachment from the body can be prevented. In other words, the cured product of the curable composition has the adhesiveness excellent in heat resistance and water resistance to the adherend because the cationic polymerization initiator is used.

  Moreover, in the conventional curable composition, the cationic polymerization initiator and alkali metal which are contained in it formed a salt. Therefore, there exists a problem that the light transmittance of the to-be-adhered body containing an alkali metal will deteriorate by using the conventional curable composition.

  On the other hand, in the curable composition of the present invention, since the water repellency of the cationic polymerization initiator is increased, salt formation between the cationic polymerization initiator and the alkali metal can be prevented, thus solving such a 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.

  Therefore, for example, as described later, the curable composition of the present invention can be very usefully used as an adhesive for members of optical devices. Other uses of the curable composition of the present invention include display adhesives such as liquid crystal displays, coating agents for various materials such as paints, metals and plastics, sealants, sealants and the like.

  In the present specification, “shrinkage stress” refers to a force generated on a cured product to shrink. In addition, the “adhered body” means a material 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.

  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, and examples thereof include the use of the curable composition of the present invention for coating the members of the optical device of the present invention. 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 “using the curable composition of the present invention for coating the member of the optical device of the present invention” means, for example, using the curable composition of the present invention by 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 the conventional curable composition, the cationic polymerization initiator and alkali metal contained therein formed a salt. Therefore, there is a problem that 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, or light transmittance between the cured product and the member is deteriorated. there were. On the other hand, since the curable composition of the present invention contains a cationic polymerization initiator capable of greatly reducing salt formation with an alkali metal as described above, such a problem can be solved. Therefore, the curable composition of the present invention is very useful in terms of reducing the separation between the cured product and the member and maintaining the light transmittance between the cured product and the member.

  In addition, a curable composition hardens | cures by irradiating light or applying heat to the curable composition of this invention, and members can be adhere | attached by this hardening. Accordingly, when the members are bonded by irradiating light, at least one of the members that can be bonded is a material having a material that can transmit light, such as the above-described quartz or organic material (hereinafter referred to as a material that transmits light). , Described as “light transmissive material”). 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 members are bonded together by applying heat, the bonded members are made of a material having a material that can withstand the heating (hereinafter referred to as “heat-resistant material”). preferable. 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.

  Moreover, the curable composition of this invention can be used for adhesion | attachment of the members whose adhesion interface is uneven | corrugated shape. The above “adhesive interface is uneven” 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, the optical device of the present invention will be described with reference to 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.

  According to said structure, since 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 as above-mentioned, in a high temperature environment or It is possible to prevent a decrease in the adhesive strength between members even in a high temperature and humidity environment. Therefore, an optical device having excellent heat resistance and moisture resistance can be produced.

  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 said adhesion process, a curable composition can be hardened by irradiating light to the curable composition of this invention through a member, and members can be adhere | attached. 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. Moreover, it does not specifically limit as a method of irradiating a curable composition with an ultraviolet-ray, For example, the method of using a low pressure or a high pressure mercury lamp, a metal halide lamp, a xenon lamp etc. is mentioned. When ultraviolet rays are used, the wavelength range is not particularly limited, but is preferably 150 nm to 400 nm, and more preferably 200 nm to 380 nm.

  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 spectrophotometer or a photochemical reaction calorimeter, the curing conditions for completely curing the cured product (light irradiation time, light intensity, heating) Temperature, heating time, etc.) can be selected as appropriate.

  The present invention is not limited to the above-described embodiments, and various modifications can be made 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]
<Manufacture of curable composition>
Each component was mixed in the ratio shown in the following Table 1, and the curable composition was manufactured.

  That is, 50 parts by weight of OXT-221 (manufactured by Toagosei Co., Ltd.) as a reaction accelerator with respect to 50 parts by weight of a hydrogenated bisphenol A type epoxy (Japan Epoxy Resin Co., Ltd .: jER YX-8000) as a cationic polymerizable compound, And 1.5 parts by weight of triphenylsulfonium phosphate represented by the above formula (1) (manufactured by San Apro Co., Ltd .: K-1S) as a cationic polymerization initiator was added and stirred and mixed uniformly, and then defoamed. Then, a curable composition was produced.

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

  50 parts by weight of OXT-221 (manufactured by Toagosei Co., Ltd.) as a reaction accelerator for 50 parts by weight of a hydrogenated bisphenol A type epoxy compound (manufactured by Japan Epoxy Resin Co., Ltd .: jER YX-8000) as a cationic polymerizable compound, 1.5 parts by weight of triphenylsulfonium phosphate represented by the above formula (1) as a polymerizable compound (manufactured by San-Apro: K-1S) and a silane coupling agent (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.) as an additive After adding 5 parts by weight and stirring and mixing uniformly, the mixture was defoamed to produce a curable composition.

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

  An epoxy compound having a polybutadiene structure as a flexibility-imparting material (manufactured by Nippon Soda Co., Ltd., EPB-) with respect to 25 parts by weight of a hydrogenated bisphenol A type epoxy compound (manufactured by Japan Epoxy Resin: jER YX-8000) as a cationic polymerizable compound 13) 25 parts by weight, OXT-221 (manufactured by Toagosei Co., Ltd.) as a reaction accelerator, 50 parts by weight, and triphenylsulfonium phosphate represented by the above formula (1) as a cationic polymerizable compound (manufactured by San Apro: Add 1.5 parts by weight of K-1S) and 5 parts by weight of a silane coupling agent (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.) as an additive, and after stirring and mixing uniformly, defoaming to produce a curable composition did.

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

  An epoxy compound having a polybutadiene structure as a flexibility-imparting material (manufactured by Nippon Soda Co., Ltd .: EPB-) with respect to 25 parts by weight of a hydrogenated bisphenol A type epoxy compound (manufactured by Japan Epoxy Resin Co., Ltd .: jER YX-8000) as a cationic polymerizable compound 13) 25 parts by weight, OXT-221 (manufactured by Toagosei Co., Ltd.) as a reaction accelerator, 50 parts by weight, carboxy-terminated butadiene nitrile rubber modified bisphenol A epoxy compound (Dainippon Ink Co., Ltd.) as a reaction accelerator and adhesion improver 15 parts by weight of Epiclon TSR-960), 1.5 parts by weight of triphenylsulfonium phosphate represented by the above formula (1) as a cationically polymerizable compound (manufactured by San Apro: K-1S), and additives Silane coupling agent (Shin-Etsu Chemical Co., Ltd .: KBM403) Was added parts by weight were uniformly stirred and mixed, defoamed, to prepare a curable composition.

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

  Instead of 1.5 parts by weight of triphenylsulfonium phosphate represented by the formula (1) (manufactured by San Apro: K-1S), a 50 wt% propylene carbonate solution of triphenylsulfonium hexafluorophosphoric acid (Adekaoptomer SP150) ) Was added in the same manner as in Example 1 except that 3 parts by weight of) was added.

<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 2]
<Preparation of curable composition>
Instead of 1.5 parts by weight of triphenylsulfonium phosphate represented by the formula (1) (manufactured by San Apro: K-1S), a 50 wt% propylene carbonate solution of triphenylsulfonium hexafluorophosphoric acid (Adekaoptomer SP150) ) Was added in the same manner as in Example 2 except that 3 parts by weight of) was added.

<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 3]
<Manufacture of curable composition>
Instead of 1.5 parts by weight of triphenylsulfonium phosphate represented by the above formula (1) (manufactured by San Apro: K-1S), a 50 wt% propylene carbonate solution of triphenylsulfonium hexafluorophosphoric acid (Adekaoptomer SP150) ) Was added in the same manner as in Example 3 except that 3 parts by weight of) was added.

<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 4]
<Manufacture of curable composition>
Instead of 1.5 parts by weight of triphenylsulfonium phosphate represented by the formula (1) (manufactured by San Apro: K-1S), a 50 wt% propylene carbonate solution of triphenylsulfonium hexafluorophosphoric acid (Adekaoptomer SP150) A curable composition was produced in the same manner as in Example 4 except that 3 parts by weight) was added.

<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 has shown the ratio of each component of the structural compound of the curable composition of Examples 1-4 and Comparative Examples 1-4 by the weight part.

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

  From Table 2, when compared with the cured products of Comparative Examples 1 to 4, the cured products of Examples 1 to 4 have a small decrease in the adhesive strength after the high-temperature and high-humidity test, retain a strong adhesive strength, and have excellent adhesive properties. You can see that it has.

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

  From Table 3, when compared with the cured products of Comparative Examples 1 to 4, the cured products of Examples 1 to 4 have a small increase in Young's modulus after the high temperature and high humidity test, and the curing reaction that occurs in the high temperature and high humidity is small. I understand. When combined with the results shown in Table 2 above, it can be seen that the cured products of Examples 1 to 4 have less curing in high temperature and high humidity than the cured products of Comparative Examples 1 to 4, and thus the decrease in adhesion is small.

  The cured product of the curable composition of the present invention does not deteriorate or peel off even in a high temperature environment or a high temperature and high humidity environment. Therefore, the curable composition of the present invention can be suitably used as an adhesive, paint, or coating agent for display devices such as optical devices and liquid crystals. Therefore, the present invention is applied to an 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 in WDM (optical wavelength division multiplexing) and a display display manufacturing industry such as a liquid crystal. It can be used.

(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 (9)

A curable composition containing a cationic polymerizable compound and a cationic polymerization initiator represented by the general formula (1), wherein the cured product of the curable composition is held at 121 ° C. or 121 ° C. and 100 RH% for 48 hours. A curable composition having a change in Young's modulus before and after being 1.0 or more and 1.5 or less.

(In formula (1), R _{1 to} R ₃ each independently represents an aryl group, a heterocyclic group, or an alkyl group. Rf represents an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms. X, m, and n are integers of m = 6 and n = 1 to 5 when X is P, m = 6 when X is Sb, integers of n = 1 to 5, and m = when X is B 4, n is an integer of 1 to 3.)   The curable composition according to claim 1, wherein the cationic polymerizable compound is one or more compounds selected from the group consisting of an epoxy compound, an oxetane compound, and a vinyl ether compound.   The curable composition according to claim 1, wherein the cationically polymerizable compound contains an epoxy compound and an oxetane compound.   The epoxy compound is at least one compound selected from the group consisting of an alicyclic epoxy compound, an epoxy compound having a polybutadiene structure, a carboxy-terminated butadiene nitrile rubber-modified bisphenol A type epoxy compound, and an epoxidized polybutadiene compound. The curable composition according to claim 2 or 3, characterized in that   The curable composition according to any one of claims 2 to 4, wherein the oxetane compound has a hydroxyl group.   A silane coupling agent is further contained, The curable composition of any one of Claims 1-5 characterized by the above-mentioned.   An optical device manufactured using the curable composition according to any one of claims 1 to 6.   The optical device according to claim 7, wherein the optical device has two or more members.   9. The optical device according to claim 7, wherein the material used for the member is an organic material or synthetic quartz.

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