WO2016031602A1 - Photosensitive resin composition for optical applications and optical material using same - Google Patents
Photosensitive resin composition for optical applications and optical material using same Download PDFInfo
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- WO2016031602A1 WO2016031602A1 PCT/JP2015/072996 JP2015072996W WO2016031602A1 WO 2016031602 A1 WO2016031602 A1 WO 2016031602A1 JP 2015072996 W JP2015072996 W JP 2015072996W WO 2016031602 A1 WO2016031602 A1 WO 2016031602A1
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- resin composition
- optical
- photosensitive resin
- cyclic hydrocarbon
- polymerizable compound
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Definitions
- the present invention is a transparent resin for optical applications, has high transparency that allows optical signals to pass through with low loss, and has excellent transparency and heat resistance.
- the present invention relates to an optical photosensitive resin composition that can be widely used for materials and the like, and an optical material using the same.
- a photocurable resin composition mainly composed of an epoxy resin having a high refractive index and excellent heat resistance has attracted attention from the viewpoint of thinning an optical lens and increasing the resolution of an image.
- Patent Document 1 a photosensitive resin composition using an epoxy compound and a photocationic polymerization initiator has been proposed.
- the photocurable resin composition mainly composed of an epoxy compound such as the photosensitive resin composition described in Patent Document 1
- the refractive index is improved, the Abbe number is significantly reduced because the wavelength dependency of the refractive index is large.
- the resin composition having highly refractive nano-oxide fine particles described in Patent Document 2 can significantly improve the refractive index, but the resin becomes clouded due to the dispersibility of the nano-oxide fine particles. As a result, it was difficult to use as an optical material.
- the present invention has been made in view of such circumstances, and has an optical photosensitive resin composition suitable for an optical material having a high refractive index and a high Abbe number and having high transparency, and an optical material using the same.
- the purpose is to provide
- the first gist of the present invention is an optical photosensitive resin composition containing the following (A) and (B).
- (A) A cationically polymerizable compound having a crosslinked cyclic hydrocarbon structure.
- (B) A photoacid generator.
- the second gist of the present invention is an optical material obtained by curing the optical photosensitive resin composition of the first gist.
- the inventors of the present invention have made extensive studies in order to obtain an optical photosensitive resin composition having a high refractive index and a high Abbe number.
- a cationically polymerizable compound having a special skeleton structure having a crosslinked cyclic hydrocarbon structure is used, high transparency and low molecules in the visible light region due to the crosslinked cyclic hydrocarbon structure are used.
- Dispersion [specifically, ⁇ R in the following formula (a).
- R represents molecular refraction
- n D represents the refractive index of sodium D line
- V D represents the Abbe number.
- the present invention is an optical photosensitive resin composition containing the special cationically polymerizable compound (A) having the above-mentioned crosslinked cyclic hydrocarbon structure and the photoacid generator (B).
- cured material formed by photocuring using this resin composition has a high Abbe number with a high refractive index.
- this optical photosensitive resin composition can be photocured on a transparent substrate such as a glass plate, a high-quality hybrid lens can be produced by integrating it with the transparent substrate. Therefore, when the optical photosensitive resin composition of the present invention is used for molding materials for optical parts such as lenses and photocurable adhesives for fixing optical parts, it is possible to obtain highly reliable optical materials. It is useful because it can.
- the cationic polymerizable compound (A) is a cationic polymerizable compound having a crosslinked ring structure represented by the general formula (1) and a cationic polymerizable compound having a crosslinked ring structure represented by the general formula (2). When it is at least one of the compounds, it has a higher Abbe number as well as a higher refractive index.
- the optical photosensitive resin composition of the present invention (hereinafter sometimes referred to as a photosensitive resin composition or a resin composition) includes a special cationically polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure. And a photoacid generator (B).
- A cationically polymerizable compound having a crosslinked cyclic hydrocarbon structure.
- B photoacid generator
- the special cationic polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure has a crosslinked cyclic hydrocarbon structure in its skeleton structure, for example, an epoxy compound having a crosslinked cyclic hydrocarbon structure, or an oxetane having a crosslinked cyclic hydrocarbon structure.
- examples thereof include compounds, episulfide compounds having a bridged cyclic hydrocarbon structure, vinyl ether compounds having a bridged cyclic hydrocarbon structure, and the like. These may be used alone or in combination of two or more.
- an epoxy compound having a crosslinked cyclic hydrocarbon structure is preferably used.
- examples of the bridged cyclic hydrocarbon structure include those having a cyclopentane structure, more specifically those having a dicyclopentane structure, and examples thereof include norbornene derivatives.
- specific examples of the norbornene derivative include norbornene, norbornylene, vinyl norbornene, dicyclopentadiene, tetrahydrodicyclopentadiene, tricyclopentadiene, hexahydrotricyclopentadiene, and the like.
- the bridged cyclic hydrocarbon structure examples include a bridged ring structure represented by the following general formula (1), a bridged ring structure represented by the following general formula (2), and the like.
- the cationically polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure specifically, a cationically polymerizable compound having a crosslinked ring structure represented by the following general formula (1), the following general formula: Examples thereof include a cationically polymerizable compound having a crosslinked ring structure represented by (2). These may be used alone or in combination.
- X is an oxygen atom
- Y is an oxygen atom
- m is 1
- n is 2.
- X is particularly preferably an oxygen atom
- Y is an oxygen atom.
- cationic polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure examples include Adeka Resin EP-4088S, EP as cationic polymerizable compounds having a crosslinked ring structure represented by the general formula (1).
- -4088L all manufactured by ADEKA
- dicyclopentadiene diepoxide manufactured by Synquest
- the like as the cationically polymerizable compound having a crosslinked ring structure represented by the general formula (2).
- a cationic polymerizable compound having no crosslinked cyclic hydrocarbon structure can be used in combination with the above (A).
- Combined use of the cationic polymerizable compound not having the above-mentioned crosslinked cyclic hydrocarbon structure produces effects of adjusting the polymerization rate and further increasing the refractive index.
- Examples of the cationic polymerizable compound having no crosslinked cyclic hydrocarbon structure include an epoxy compound, an oxetane compound, an episulfide compound, and a vinyl ether compound. These can be used alone or in combination of two or more.
- the epoxy compound examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins and the like, phenol novolacs, and the like.
- examples thereof include novolak type epoxy resins such as type epoxy resins, alicyclic epoxy resins such as linear aliphatic type epoxy resins, dicyclocyclic type epoxy resins, and fluorene type epoxy resins.
- an epoxy compound containing no aromatic ring is preferably used from the viewpoint of achieving both a high refractive index and a high Abbe number.
- oxetane compound examples include bis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, xylylenebisoxetane, 4,4′-bis (3- Methyloxetane-3-ylmethyloxymethyl) biphenyl and the like.
- an oxetane compound containing no aromatic ring is preferably used from the viewpoint of achieving both a high refractive index and a high Abbe number.
- episulfide compound examples include SR100H (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
- examples of the vinyl ether compound include ethyl vinyl ether, isobutyl vinyl ether, hydroxybutyl vinyl ether, butanediol divinyl ether, cyclohexyl vinyl ether, N-butyl vinyl ether, tert-butyl vinyl ether, triethylene glycol divinyl ether octadecyl vinyl ether, cyclohexane dimethanol dimer.
- examples thereof include vinyl ether, diethylene glycol divinyl ether, cyclohexane dimethanol monovinyl ether (all manufactured by BASF Japan).
- a vinyl ether compound containing no aromatic ring is preferably used from the viewpoint of achieving both a high refractive index and a high Abbe number.
- the content of the cationic polymerizable compound not having the above-mentioned crosslinked cyclic hydrocarbon structure is set to 0 to 50 parts by weight with respect to 100 parts by weight of the solid content of the varnish (liquid resin composition). And more preferably 5 to 30 parts by weight. That is, if the content of the cationically polymerizable compound having no crosslinked cyclic hydrocarbon structure is too small, satisfactory photocurability by light irradiation (ultraviolet irradiation) is difficult to obtain, and if the content is too large, There is a tendency that the rate and the Abbe number are lowered, or the characteristics as an optical material as a cured body are impaired.
- the photo acid generator (photo cationic polymerization initiator) (B) is used for imparting curability to the photosensitive resin composition by light irradiation (for example, ultraviolet irradiation).
- an onium salt photoacid generator (photocation polymerization initiator) such as sulfonium salt or iodonium salt can be used.
- anion component in the onium salt system examples include phosphate ions such as PF 6 ⁇ and PF 4 (CF 2 CF 3 ) 2 — , antimonate ions such as SbF 6 — , and fluoroalkyl sulfones such as trifluoromethanesulfonate. Examples include acid ions.
- Examples of the cation component in the onium salt system include sulfonium such as aromatic sulfonium, iodonium such as aromatic iodonium, phosphonium such as aromatic phosphonium, sulfoxonium such as aromatic sulfoxonium, and the like.
- an onium salt examples include a sulfonium salt such as an aromatic sulfonium salt, an iodonium salt such as an aromatic iodonium salt, a phosphonium salt such as an aromatic phosphonium salt, and an aromatic sulfoxo having the anion component as a counter anion.
- a sulfonium salt such as an aromatic sulfonium salt
- an iodonium salt such as an aromatic iodonium salt
- a phosphonium salt such as an aromatic phosphonium salt
- an aromatic sulfoxo having the anion component as a counter anion.
- examples thereof include sulfoxonium salts such as nium salts.
- Such photoacid generators (B) can be used alone or in combination of two or more.
- aromatic sulfonium salt photoacid generators are preferably used.
- the content of the photoacid generator (B) is preferably set to 0.1 to 3 parts by weight, more preferably 0.2 to 100 parts by weight of the solid content of the varnish (liquid resin composition). To 1 part by weight. That is, if the content of the photoacid generator (B) is too small, satisfactory photocurability by light irradiation (ultraviolet irradiation) is difficult to obtain, and if the content is too large, the cured photosensitive resin composition There is a tendency to cause coloring and impair the properties as an optical material.
- the exposure sensitivity can be improved.
- the photosensitizer for example, thioxanthone, anthracene, acetophenone, benzophenone or the like having an absorption wavelength in the ultraviolet region can be used. Since the sensitizing effect of these photosensitizers depends on the oxidation potential of the photoacid generator (B) and the reduction potential of the photosensitizer, it is preferable to select and use an optimal combination appropriately in consideration of these. .
- photosensitizers having absorption in the visible region such as phenothiazine, methylene blue, and rose bengal also show a sensitizing effect, but these are not suitable for use because they impair the transparency of the cured photosensitive resin composition.
- the content of the photosensitizer is preferably set to 0.01 to 3.0 parts by weight, more preferably 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the solid content of the varnish (liquid resin composition). 1.0 part by weight.
- photocurability by satisfactory light irradiation is hard to be obtained, and when there is too much content, the cause of coloring of the photosensitive resin composition hardening body is obtained. As a result, the properties as an optical material are impaired.
- an acid proliferating agent can be blended in the optical photosensitive resin composition of the present invention for the purpose of further improving curability.
- a silane or titanate cup is used to improve the adhesion between the transparent substrate and the optical material.
- a ring agent may be added.
- a flexibility imparting agent such as a synthetic rubber or a silicone compound, an antioxidant, an antifoaming agent, or the like can be blended at an appropriate ratio according to the purpose and application.
- inorganic additives such as various pigments, dyes, and inorganic fillers can be appropriately blended as necessary.
- the optical photosensitive resin composition of the present invention is prepared, for example, by blending the above-mentioned (A) and (B), and other additives as necessary, at a predetermined ratio, and heat-melt mixing. be able to.
- the optical photosensitive resin composition of the present invention is used, for example, as follows. That is, the resin composition is potted on a transparent substrate such as glass, and a desired molding die is pressed onto the resin composition to fill the resin composition into the molding die, and light is irradiated there. It can be cured by doing so. Then, by removing the molding die, a cured body of the resin composition integrated on the transparent substrate (an optical material that is a molded product) can be obtained. Alternatively, the resin composition can be filled into a transparent mold that transmits light and photocured.
- the optical photosensitive resin composition of the present invention can produce, for example, a hybrid lens by such a production method.
- the optical photosensitive resin composition of the present invention can be cured by itself in a molding die to be an optical component such as an optical lens. Furthermore, you may heat-process at the predetermined temperature with respect to the said hardening body after the said light irradiation as needed. By the heating, the heat resistance stability of the cured body can be improved, and particularly in the case of a laminate with a transparent substrate, the adhesion between the substrate and the cured resin can be improved.
- an ultraviolet (UV) lamp or a single band lamp having a specific wavelength can be used as an apparatus.
- the irradiation amount is preferably, for example, 2000 to 50000 mJ / cm 2 , more preferably 2000 to 30000 mJ / cm 2 . That is, when the irradiation amount is less than the above range, it is difficult to sufficiently cure the photosensitive resin composition, and it tends to be difficult to mold the obtained optical material into a desired cured product shape on the transparent substrate. It is done. Moreover, it is because there exists a possibility that the malfunction that photodegradation will arise by excessive irradiation may arise when it exceeds the said range.
- the photosensitive resin composition can be sufficiently cured when the irradiation amount is within the above range, for example, the photosensitive resin composition can be molded into a desired cured product shape on a transparent substrate, Moreover, it becomes possible to prevent the light deterioration by excessive irradiation.
- the heat treatment temperature is preferably 50 to 200 ° C., more preferably 80 to 170 ° C.
- the heat treatment time is preferably 0. .5-3 hours, more preferably 0.5-2 hours.
- optical photosensitive resin composition of the present invention can be molded into a sheet shape regardless of the above-described molding die.
- optical photosensitive resin composition of the present invention obtained as described above can be used as a molding material (optical material) for optical components by mounting it on a printed circuit board or the like by solder reflow.
- the optical photosensitive resin composition of the present invention can be used as a molding material (optical material) for optical parts such as optical lenses by the production method as described above, and is also a light curing type for fixing optical waveguides and optical parts. It can be used for various applications such as adhesives.
- each cationic polymerizable compound, photoacid generator, and silane coupling agent shown below were prepared.
- C-1 Hydrogenated bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, YX8000)
- C-2 3-ethyl-3 ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane (manufactured by Toagosei Co., Ltd., OXT-221)
- C-3 2-Phenylphenol glycidyl ether (manufactured by Sanko Co., Ltd., OPP-G)
- the example product using the cationic polymerizable compound having a crosslinked cyclic hydrocarbon structure showed a high refractive index and a high Abbe number. Therefore, it is possible to provide an optical material such as an optical lens having a high refractive index and a high Abbe number by using the optical photosensitive resin composition of the example product.
- the comparative example product was an embodiment using a conventional cationic polymerizable compound, and both the refractive index and the Abbe number were lower than those of the example product.
- the optical photosensitive resin composition of the present invention can be a three-dimensionally shaped product (cured product) having a high refractive index and a high Abbe number while having high transparency. Therefore, it is a molding material for optical components such as optical lenses. It is useful for optical applications such as (optical material) and a photo-curing adhesive for fixing optical components. Moreover, since the optical material using the optical photosensitive resin composition of the present invention has high reliability, it can be used for optical products such as optical lenses.
Abstract
The present invention is a photosensitive resin composition for optical applications, which contains a cationically polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure and a photoacid generator (B). Consequently, a cured body which is obtained by photocuring this photosensitive resin composition for optical applications achieves high refractive index and high Abbe number. Since this photosensitive resin composition for optical applications is able to be photocured on a transparent substrate such as a glass plate, it is possible to produce a high-quality hybrid lens by integrating this photosensitive resin composition for optical applications with the transparent substrate. Consequently, in cases where this photosensitive resin composition for optical applications is used as a molding material for optical components such as lenses, a photocurable adhesive for optical component fixation, and the like, this photosensitive resin composition for optical applications is useful for the achievement of a good optical material that has high reliability.
Description
本発明は、光学的応用を目的とする透明樹脂において光信号を低損失で通す高い透明性を有し、耐熱性に優れた光学レンズや集光拡散レンズ、光学部品間の接着等、各種光学材料等に広く利用可能な光学用感光性樹脂組成物およびそれを用いた光学材料に関するものである。
The present invention is a transparent resin for optical applications, has high transparency that allows optical signals to pass through with low loss, and has excellent transparency and heat resistance. The present invention relates to an optical photosensitive resin composition that can be widely used for materials and the like, and an optical material using the same.
従来から、光学部品用の接着剤、シーリング材、フィルター、光学レンズの材料として、種々の材料が検討されている。このような材料において、光学レンズの薄型化や、画像の高解像度化の観点から、高屈折率および耐熱性に優れたエポキシ樹脂を主成分とする光硬化性樹脂組成物が注目されている。
Conventionally, various materials have been studied as materials for adhesives, sealing materials, filters, and optical lenses for optical components. Among such materials, a photocurable resin composition mainly composed of an epoxy resin having a high refractive index and excellent heat resistance has attracted attention from the viewpoint of thinning an optical lens and increasing the resolution of an image.
このような光硬化性樹脂組成物としては、例えば、エポキシ化合物、光カチオン重合開始剤を用いた感光性樹脂組成物が提案されている（特許文献１）。
As such a photocurable resin composition, for example, a photosensitive resin composition using an epoxy compound and a photocationic polymerization initiator has been proposed (Patent Document 1).
一方、これらの光学部品用の光硬化性樹脂組成物としては、光学材料として使用される光学装置の小型・低背化に伴って、さらなる高屈折および高アッベ数化が求められるようになっていきている。このことから、例えば、高屈折のナノ酸化物微粒子を含有する樹脂組成物が提案されており（特許文献２）、これを用いることにより、屈折率の向上を図ることが考えられる。
On the other hand, as a photocurable resin composition for these optical components, as the optical device used as an optical material is reduced in size and height, further higher refraction and higher Abbe number are required. living. From this, for example, a resin composition containing highly refractive nano-oxide fine particles has been proposed (Patent Document 2), and it is conceivable to improve the refractive index by using this.
しかしながら、上記特許文献１に記載の感光性樹脂組成物のような、エポキシ化合物を主成分とする光硬化性樹脂組成物は、屈折率向上のために、芳香環式エポキシ樹脂を用いているため、屈折率の向上はみられるが、その屈折率の波長依存性が大きいためアッベ数は顕著に低下することとなる。
However, since the photocurable resin composition mainly composed of an epoxy compound, such as the photosensitive resin composition described in Patent Document 1, uses an aromatic ring epoxy resin for improving the refractive index. Although the refractive index is improved, the Abbe number is significantly reduced because the wavelength dependency of the refractive index is large.
また、上記特許文献２に記載の高屈折のナノ酸化物微粒子を有する樹脂組成物では、屈折率の大幅な向上効果は得られるが、上記ナノ酸化物微粒子の分散性に起因する樹脂の白濁化がみられ、光学材料としての用途での使用は困難であった。
In addition, the resin composition having highly refractive nano-oxide fine particles described in Patent Document 2 can significantly improve the refractive index, but the resin becomes clouded due to the dispersibility of the nano-oxide fine particles. As a result, it was difficult to use as an optical material.
本発明は、このような事情に鑑みてなされたもので、高屈折率と高アッベ数を備え、高い透明性を有する光学材料として好適な光学用感光性樹脂組成物およびそれを用いた光学材料の提供をその目的とする。
The present invention has been made in view of such circumstances, and has an optical photosensitive resin composition suitable for an optical material having a high refractive index and a high Abbe number and having high transparency, and an optical material using the same. The purpose is to provide
上記の目的を達成するため、本発明は、下記の（Ａ）および（Ｂ）を含有する光学用感光性樹脂組成物を第１の要旨とする。
（Ａ）架橋環式炭化水素構造を有するカチオン重合性化合物。
（Ｂ）光酸発生剤。 To achieve the above object, the first gist of the present invention is an optical photosensitive resin composition containing the following (A) and (B).
(A) A cationically polymerizable compound having a crosslinked cyclic hydrocarbon structure.
(B) A photoacid generator.
（Ａ）架橋環式炭化水素構造を有するカチオン重合性化合物。
（Ｂ）光酸発生剤。 To achieve the above object, the first gist of the present invention is an optical photosensitive resin composition containing the following (A) and (B).
(A) A cationically polymerizable compound having a crosslinked cyclic hydrocarbon structure.
(B) A photoacid generator.
また、本発明は、上記第１の要旨の光学用感光性樹脂組成物を硬化させることにより得られてなる光学材料を第２の要旨とする。
The second gist of the present invention is an optical material obtained by curing the optical photosensitive resin composition of the first gist.
本発明者らは、高屈折率を有し、かつ高アッベ数をも備えた光学用感光性樹脂組成物を得るために鋭意検討を重ねた。その結果、カチオン重合性化合物として、架橋環式炭化水素構造を有する特殊な骨格構造を備えたものを用いると、上記架橋環式炭化水素構造に起因した、可視光領域における高い透明性と低い分子分散〔具体的には、下記の数式（ａ）におけるΔＲをいう。なお、式（ａ）中、Ｒは分子屈折、ｎDはナトリウムＤ線の屈折率、ＶDはアッベ数を示す。〕という作用効果を奏することから所期の目的を達成することが可能となり、高い透明性を有しながら、硬化後屈折率が高いことはもちろん、アッベ数も従来に比べて高い物性を有する硬化体を得ることのできる樹脂組成物が得られることを見出し本発明に到達した。
The inventors of the present invention have made extensive studies in order to obtain an optical photosensitive resin composition having a high refractive index and a high Abbe number. As a result, when a cationically polymerizable compound having a special skeleton structure having a crosslinked cyclic hydrocarbon structure is used, high transparency and low molecules in the visible light region due to the crosslinked cyclic hydrocarbon structure are used. Dispersion [specifically, ΔR in the following formula (a). In the formula (a), R represents molecular refraction, n D represents the refractive index of sodium D line, and V D represents the Abbe number. It is possible to achieve the intended purpose because of the operational effects of the above, and while having high transparency, the refractive index after curing is high, and of course, the Abbe number has higher physical properties than before. The present inventors have found that a resin composition capable of obtaining a body is obtained, and have reached the present invention.
このように、本発明は、上記架橋環式炭化水素構造を有する特殊なカチオン重合性化合物（Ａ）および光酸発生剤（Ｂ）を含有する光学用感光性樹脂組成物である。このため、この樹脂組成物を用いて光硬化してなる硬化体は、高屈折率とともに高アッベ数を備えたものが得られる。そして、この光学用感光性樹脂組成物はガラス板等の透明基板上で光硬化させることができることから、上記透明基板と一体化させることにより高品質なハイブリッドレンズを製造することも可能である。したがって、本発明の光学用感光性樹脂組成物を、レンズ等の光学部品用の成形材料および光学部品固定用光硬化型接着剤等に用いる場合、高信頼性の良好な光学材料を得ることができるため有用である。
Thus, the present invention is an optical photosensitive resin composition containing the special cationically polymerizable compound (A) having the above-mentioned crosslinked cyclic hydrocarbon structure and the photoacid generator (B). For this reason, the hardened | cured material formed by photocuring using this resin composition has a high Abbe number with a high refractive index. And since this optical photosensitive resin composition can be photocured on a transparent substrate such as a glass plate, a high-quality hybrid lens can be produced by integrating it with the transparent substrate. Therefore, when the optical photosensitive resin composition of the present invention is used for molding materials for optical parts such as lenses and photocurable adhesives for fixing optical parts, it is possible to obtain highly reliable optical materials. It is useful because it can.
そして、上記カチオン重合性化合物（Ａ）が、一般式（１）で表される架橋環構造を有するカチオン重合性化合物、および、一般式（２）で表される架橋環構造を有するカチオン重合性化合物の少なくとも一方であると、より一層高屈折率とともに高アッベ数を有するようになる。
The cationic polymerizable compound (A) is a cationic polymerizable compound having a crosslinked ring structure represented by the general formula (1) and a cationic polymerizable compound having a crosslinked ring structure represented by the general formula (2). When it is at least one of the compounds, it has a higher Abbe number as well as a higher refractive index.
つぎに、本発明の実施の形態について詳しく説明する。ただし、本発明は、この実施の形態に限定されるものではない。
Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to this embodiment.
《光学用感光性樹脂組成物》
本発明の光学用感光性樹脂組成物（以下、感光性樹脂組成物、もしくは、樹脂組成物という場合がある。）は、架橋環式炭化水素構造を有する特殊なカチオン重合性化合物（Ａ）と、光酸発生剤（Ｂ）を用いて得られるものである。
以下、各種成分について順に説明する。 << Optical photosensitive resin composition >>
The optical photosensitive resin composition of the present invention (hereinafter sometimes referred to as a photosensitive resin composition or a resin composition) includes a special cationically polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure. And a photoacid generator (B).
Hereinafter, various components will be described in order.
本発明の光学用感光性樹脂組成物（以下、感光性樹脂組成物、もしくは、樹脂組成物という場合がある。）は、架橋環式炭化水素構造を有する特殊なカチオン重合性化合物（Ａ）と、光酸発生剤（Ｂ）を用いて得られるものである。
以下、各種成分について順に説明する。 << Optical photosensitive resin composition >>
The optical photosensitive resin composition of the present invention (hereinafter sometimes referred to as a photosensitive resin composition or a resin composition) includes a special cationically polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure. And a photoacid generator (B).
Hereinafter, various components will be described in order.
＜架橋環式炭化水素構造を有する特殊なカチオン重合性化合物（Ａ）＞
上記特殊なカチオン重合性化合物（Ａ）は、その骨格構造に架橋環式炭化水素構造を有するものであり、例えば、架橋環式炭化水素構造を有するエポキシ化合物、架橋環式炭化水素構造を有するオキセタン化合物、架橋環式炭化水素構造を有するエピスルフィド化合物および架橋環式炭化水素構造を有するビニルエーテル化合物等があげられる。これらは単独でもしくは二種以上併せて用いられる。特に反応性と合成という観点から、架橋環式炭化水素構造を有するエポキシ化合物が好適に使用される。 <Special cationically polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure>
The special cationic polymerizable compound (A) has a crosslinked cyclic hydrocarbon structure in its skeleton structure, for example, an epoxy compound having a crosslinked cyclic hydrocarbon structure, or an oxetane having a crosslinked cyclic hydrocarbon structure. Examples thereof include compounds, episulfide compounds having a bridged cyclic hydrocarbon structure, vinyl ether compounds having a bridged cyclic hydrocarbon structure, and the like. These may be used alone or in combination of two or more. In particular, from the viewpoints of reactivity and synthesis, an epoxy compound having a crosslinked cyclic hydrocarbon structure is preferably used.
上記特殊なカチオン重合性化合物（Ａ）は、その骨格構造に架橋環式炭化水素構造を有するものであり、例えば、架橋環式炭化水素構造を有するエポキシ化合物、架橋環式炭化水素構造を有するオキセタン化合物、架橋環式炭化水素構造を有するエピスルフィド化合物および架橋環式炭化水素構造を有するビニルエーテル化合物等があげられる。これらは単独でもしくは二種以上併せて用いられる。特に反応性と合成という観点から、架橋環式炭化水素構造を有するエポキシ化合物が好適に使用される。 <Special cationically polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure>
The special cationic polymerizable compound (A) has a crosslinked cyclic hydrocarbon structure in its skeleton structure, for example, an epoxy compound having a crosslinked cyclic hydrocarbon structure, or an oxetane having a crosslinked cyclic hydrocarbon structure. Examples thereof include compounds, episulfide compounds having a bridged cyclic hydrocarbon structure, vinyl ether compounds having a bridged cyclic hydrocarbon structure, and the like. These may be used alone or in combination of two or more. In particular, from the viewpoints of reactivity and synthesis, an epoxy compound having a crosslinked cyclic hydrocarbon structure is preferably used.
ここで、上記架橋環式炭化水素構造としては、シクロペンタン構造を有するもの、さらに詳しくはジシクロペンタン構造を有するものがあげられ、例えば、ノルボルネン誘導体があげられる。上記ノルボルネン誘導体としては、具体的には、ノルボルネン、ノルボルニレン、ビニルノルボルネン、ジシクロペンタジエン、テトラヒドロジシクロペンタジエン、トリシクロペンタジエン、ヘキサヒドロトリシクロペンタジエン等があげられる。
Here, examples of the bridged cyclic hydrocarbon structure include those having a cyclopentane structure, more specifically those having a dicyclopentane structure, and examples thereof include norbornene derivatives. Specific examples of the norbornene derivative include norbornene, norbornylene, vinyl norbornene, dicyclopentadiene, tetrahydrodicyclopentadiene, tricyclopentadiene, hexahydrotricyclopentadiene, and the like.
そして、上記架橋環式炭化水素構造としては、具体的には、下記の一般式（１）で表される架橋環構造、下記の一般式（２）で表される架橋環構造等があげられる。従って、架橋環式炭化水素構造を有するカチオン重合性化合物（Ａ）としては、具体的には、下記の一般式（１）で表される架橋環構造を有するカチオン重合性化合物、下記の一般式（２）で表される架橋環構造を有するカチオン重合性化合物があげられる。これらは単独でもしくは併せて用いられる。
Specific examples of the bridged cyclic hydrocarbon structure include a bridged ring structure represented by the following general formula (1), a bridged ring structure represented by the following general formula (2), and the like. . Accordingly, as the cationically polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure, specifically, a cationically polymerizable compound having a crosslinked ring structure represented by the following general formula (1), the following general formula: Examples thereof include a cationically polymerizable compound having a crosslinked ring structure represented by (2). These may be used alone or in combination.
上記式（１）において、特に好ましくは、Ｘは酸素原子、Ｙは酸素原子であり、ｍは１、ｎは２である。また、上記式（２）において、特に好ましくは、Ｘは酸素原子、Ｙは酸素原子である。さらには、式（１）で表される架橋環構造を有するカチオン重合性化合物を用いることが好ましい。
In the above formula (1), particularly preferably, X is an oxygen atom, Y is an oxygen atom, m is 1, and n is 2. In the above formula (2), X is particularly preferably an oxygen atom and Y is an oxygen atom. Furthermore, it is preferable to use a cationically polymerizable compound having a crosslinked ring structure represented by the formula (1).
上記架橋環式炭化水素構造を有するカチオン重合性化合物（Ａ）としては、具体的には、上記一般式（１）で表される架橋環構造を有するカチオン重合性化合物としてアデカレジンＥＰ－４０８８Ｓ、ＥＰ－４０８８Ｌ（いずれもＡＤＥＫＡ社製）等が、また上記一般式（２）で表される架橋環構造を有するカチオン重合性化合物としてジシクロペンタジエン ジエポキシド（Ｓｙｎｑｕｅｓｔ社製）等がそれぞれあげられる。
Specific examples of the cationic polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure include Adeka Resin EP-4088S, EP as cationic polymerizable compounds having a crosslinked ring structure represented by the general formula (1). -4088L (all manufactured by ADEKA) and the like, and dicyclopentadiene diepoxide (manufactured by Synquest) and the like as the cationically polymerizable compound having a crosslinked ring structure represented by the general formula (2).
さらに、本発明においては、カチオン重合性化合物成分として、上記（Ａ）とともに、架橋環式炭化水素構造を有さないカチオン重合性化合物を併用することができる。上記架橋環式炭化水素構造を有さないカチオン重合性化合物を併用することにより、重合速度の調整やさらなる高屈折率化という効果を奏する。上記架橋環式炭化水素構造を有さないカチオン重合性化合物としては、例えば、エポキシ化合物、オキセタン化合物、エピスルフィド化合物およびビニルエーテル化合物等があげられる。これらは単独でもしくは二種以上併せて用いることができる。
Furthermore, in the present invention, as the cationic polymerizable compound component, a cationic polymerizable compound having no crosslinked cyclic hydrocarbon structure can be used in combination with the above (A). Combined use of the cationic polymerizable compound not having the above-mentioned crosslinked cyclic hydrocarbon structure produces effects of adjusting the polymerization rate and further increasing the refractive index. Examples of the cationic polymerizable compound having no crosslinked cyclic hydrocarbon structure include an epoxy compound, an oxetane compound, an episulfide compound, and a vinyl ether compound. These can be used alone or in combination of two or more.
上記エポキシ化合物としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、水素添加ビスフェノールＡ型エポキシ樹脂、水素添加ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂、直鎖脂肪族型エポキシ樹脂、ジシクロ環型エポキシ樹脂等の脂環式エポキシ樹脂、フルオレン型エポキシ樹脂等があげられる。これらの中でも、芳香族環を含まないエポキシ化合物が、高屈折率と高アッベ数の両立の観点から好適に使用される。
Examples of the epoxy compound include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins and the like, phenol novolacs, and the like. Examples thereof include novolak type epoxy resins such as type epoxy resins, alicyclic epoxy resins such as linear aliphatic type epoxy resins, dicyclocyclic type epoxy resins, and fluorene type epoxy resins. Among these, an epoxy compound containing no aromatic ring is preferably used from the viewpoint of achieving both a high refractive index and a high Abbe number.
上記オキセタン化合物としては、例えば、ビス（３－エチル－３－オキセタニルメチル）エーテル、３－エチル－３－ヒドロキシメチルオキセタン、２－エチルヘキシルオキセタン、キシリレンビスオキセタン、４，４′－ビス（３－メチルオキセタン－３－イルメチルオキシメチル）ビフェニル等があげられる。これらのなかでも芳香族環を含まないオキセタン化合物が、高屈折率と高アッベ数の両立の観点から好適に使用される。
Examples of the oxetane compound include bis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, xylylenebisoxetane, 4,4′-bis (3- Methyloxetane-3-ylmethyloxymethyl) biphenyl and the like. Among these, an oxetane compound containing no aromatic ring is preferably used from the viewpoint of achieving both a high refractive index and a high Abbe number.
上記エピスルフィド化合物としては、例えば、ＳＲ１００Ｈ（日本合成化学工業社製）等があげられる。
Examples of the episulfide compound include SR100H (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
さらに、上記ビニルエーテル化合物としては、例えば、エチルビニルエーテル、イソブチルビニルエーテル、ヒドロキシブチルビニルエーテル、ブタンジオールジビニルエーテル、シクロヘキシルビニルエーテル、Ｎ－ブチルビニルエーテル、ｔｅｒｔ－ブチルビニルエーテル、トリエチレングリコールジビニルエーテルオクタデシルビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ジエチレングリコールジビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル（いずれもＢＡＳＦジャパン社製）等があげられる。ここでも芳香族環を含まないビニルエーテル化合物が、高屈折率と高アッベ数の両立の観点から好適に使用される。
Furthermore, examples of the vinyl ether compound include ethyl vinyl ether, isobutyl vinyl ether, hydroxybutyl vinyl ether, butanediol divinyl ether, cyclohexyl vinyl ether, N-butyl vinyl ether, tert-butyl vinyl ether, triethylene glycol divinyl ether octadecyl vinyl ether, cyclohexane dimethanol dimer. Examples thereof include vinyl ether, diethylene glycol divinyl ether, cyclohexane dimethanol monovinyl ether (all manufactured by BASF Japan). Again, a vinyl ether compound containing no aromatic ring is preferably used from the viewpoint of achieving both a high refractive index and a high Abbe number.
上記架橋環式炭化水素構造を有さないカチオン重合性化合物を併用する場合の含有量は、ワニス（液状の樹脂組成物）の固形分１００重量部に対して０～５０重量部に設定することが好ましく、より好ましくは５～３０重量部である。すなわち、架橋環式炭化水素構造を有さないカチオン重合性化合物の含有量が少なすぎると、満足のいく光照射（紫外線照射）による光硬化性が得られにくく、含有量が多すぎると、屈折率およびアッベ数が低下したり、硬化体である光学材料としての特性を損なうこととなる傾向がみられる。
The content of the cationic polymerizable compound not having the above-mentioned crosslinked cyclic hydrocarbon structure is set to 0 to 50 parts by weight with respect to 100 parts by weight of the solid content of the varnish (liquid resin composition). And more preferably 5 to 30 parts by weight. That is, if the content of the cationically polymerizable compound having no crosslinked cyclic hydrocarbon structure is too small, satisfactory photocurability by light irradiation (ultraviolet irradiation) is difficult to obtain, and if the content is too large, There is a tendency that the rate and the Abbe number are lowered, or the characteristics as an optical material as a cured body are impaired.
＜光酸発生剤（Ｂ）＞
上記光酸発生剤（光カチオン重合開始剤）（Ｂ）は、感光性樹脂組成物に対して光照射（例えば、紫外線照射等）による硬化性を付与するために用いられるものである。上記光酸発生剤（Ｂ）としては、例えば、スルホニウム塩系，ヨードニウム塩系等のオニウム塩系光酸発生剤（光カチオン重合開始剤）を用いることができる。 <Photoacid generator (B)>
The photo acid generator (photo cationic polymerization initiator) (B) is used for imparting curability to the photosensitive resin composition by light irradiation (for example, ultraviolet irradiation). As the photoacid generator (B), for example, an onium salt photoacid generator (photocation polymerization initiator) such as sulfonium salt or iodonium salt can be used.
上記光酸発生剤（光カチオン重合開始剤）（Ｂ）は、感光性樹脂組成物に対して光照射（例えば、紫外線照射等）による硬化性を付与するために用いられるものである。上記光酸発生剤（Ｂ）としては、例えば、スルホニウム塩系，ヨードニウム塩系等のオニウム塩系光酸発生剤（光カチオン重合開始剤）を用いることができる。 <Photoacid generator (B)>
The photo acid generator (photo cationic polymerization initiator) (B) is used for imparting curability to the photosensitive resin composition by light irradiation (for example, ultraviolet irradiation). As the photoacid generator (B), for example, an onium salt photoacid generator (photocation polymerization initiator) such as sulfonium salt or iodonium salt can be used.
上記オニウム塩系におけるアニオン成分としては、例えば、ＰＦ6
-、ＰＦ4（ＣＦ2ＣＦ3）2
-等のリン酸イオン、ＳｂＦ6
-等のアンチモン酸イオン、トリフルオロメタンスルホナート等のフルオロアルキルスルホン酸イオン等があげられる。
Examples of the anion component in the onium salt system include phosphate ions such as PF 6 − and PF 4 (CF 2 CF 3 ) 2 — , antimonate ions such as SbF 6 — , and fluoroalkyl sulfones such as trifluoromethanesulfonate. Examples include acid ions.
上記オニウム塩系におけるカチオン成分としては、例えば、芳香族スルホニウム等のスルホニウム、芳香族ヨードニウム等のヨードニウム、芳香族ホスホニウム等のホスホニウム、芳香族スルホキソニウム等のスルホキソニウム等があげられる。
Examples of the cation component in the onium salt system include sulfonium such as aromatic sulfonium, iodonium such as aromatic iodonium, phosphonium such as aromatic phosphonium, sulfoxonium such as aromatic sulfoxonium, and the like.
このようなオニウム塩としては、例えば、上記アニオン成分をカウンターアニオンとして有する、芳香族スルホニウム塩等のスルホニウム塩、芳香族ヨードニウム塩等のヨードニウム塩、芳香族ホスホニウム塩等のホスホニウム塩、芳香族スルホキソニウム塩等のスルホキソニウム塩等があげられる。
Examples of such an onium salt include a sulfonium salt such as an aromatic sulfonium salt, an iodonium salt such as an aromatic iodonium salt, a phosphonium salt such as an aromatic phosphonium salt, and an aromatic sulfoxo having the anion component as a counter anion. Examples thereof include sulfoxonium salts such as nium salts.
このような光酸発生剤（Ｂ）は、単独でもしくは二種以上併せて用いることができる。
Such photoacid generators (B) can be used alone or in combination of two or more.
そして、このような光酸発生剤（Ｂ）のなかでも、光硬化性を考慮した場合、好ましくは芳香族スルホニウム塩系の光酸発生剤が用いられる。
Of these photoacid generators (B), in consideration of photocurability, aromatic sulfonium salt photoacid generators are preferably used.
上記光酸発生剤（Ｂ）の含有量は、ワニス（液状の樹脂組成物）の固形分１００重量部に対して０．１～３重量部に設定することが好ましく、より好ましくは０．２～１重量部である。すなわち、光酸発生剤（Ｂ）の含有量が少なすぎると、満足のいく光照射（紫外線照射）による光硬化性が得られにくく、含有量が多すぎると、感光性樹脂組成物硬化体の着色の原因となり光学材料としての特性を損なう傾向がみられる。
The content of the photoacid generator (B) is preferably set to 0.1 to 3 parts by weight, more preferably 0.2 to 100 parts by weight of the solid content of the varnish (liquid resin composition). To 1 part by weight. That is, if the content of the photoacid generator (B) is too small, satisfactory photocurability by light irradiation (ultraviolet irradiation) is difficult to obtain, and if the content is too large, the cured photosensitive resin composition There is a tendency to cause coloring and impair the properties as an optical material.
さらに、上記光酸発生剤（Ｂ）とともに光増感剤を用い、これらを組み合わせることにより、露光感度の向上を図ることができる。上記光増感剤としては、例えば、紫外領域に吸収波長を有するチオキサントン、アントラセン、アセトフェノン、ベンゾフェノン等を用いることができる。これら光増感剤の増感効果は光酸発生剤（Ｂ）の酸化電位および光増感剤の還元電位に依存するため、これらを考慮して適宜最適な組み合わせを選定し使用することが好ましい。ちなみに、フェノチアジン、メチレンブルー、ローズベンガル等の可視領域に吸収を有する光増感剤も増感効果を示すが、これらは感光性樹脂組成物硬化体の透明性を損なうことから使用には適さない。
Furthermore, by using a photosensitizer together with the photoacid generator (B) and combining them, the exposure sensitivity can be improved. As the photosensitizer, for example, thioxanthone, anthracene, acetophenone, benzophenone or the like having an absorption wavelength in the ultraviolet region can be used. Since the sensitizing effect of these photosensitizers depends on the oxidation potential of the photoacid generator (B) and the reduction potential of the photosensitizer, it is preferable to select and use an optimal combination appropriately in consideration of these. . Incidentally, photosensitizers having absorption in the visible region such as phenothiazine, methylene blue, and rose bengal also show a sensitizing effect, but these are not suitable for use because they impair the transparency of the cured photosensitive resin composition.
上記光増感剤の含有量は、ワニス（液状の樹脂組成物）の固形分１００重量部に対して０．０１～３．０重量部に設定することが好ましく、より好ましくは０．０５～１．０重量部である。なお、光増感剤の含有量が少なすぎると、満足のいく光照射（紫外線照射）による光硬化性が得られにくく、含有量が多すぎると、感光性樹脂組成物硬化体の着色の原因となり光学材料としての特性を損なうことになる。
The content of the photosensitizer is preferably set to 0.01 to 3.0 parts by weight, more preferably 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the solid content of the varnish (liquid resin composition). 1.0 part by weight. In addition, when there is too little content of a photosensitizer, photocurability by satisfactory light irradiation (ultraviolet irradiation) is hard to be obtained, and when there is too much content, the cause of coloring of the photosensitive resin composition hardening body is obtained. As a result, the properties as an optical material are impaired.
本発明の光学用感光性樹脂組成物には、上記（Ａ），（Ｂ）および光増感剤以外に、例えば、さらに硬化性を高める目的で酸増殖剤を配合することができる。また、ガラス等の透明基材上に、硬化物を成形して光学材料を作製する用途においては、透明基材と光学材料との接着性の向上を図る目的で、シラン系あるいはチタネート系のカップリング剤を添加してもよい。また、その他の成分として、目的および用途に応じて、合成ゴムやシリコーン化合物等の可撓性付与剤、さらに酸化防止剤、消泡剤等を適宜の割合で配合することができる。また、各種顔料、染料、無機質充填剤等の無機添加剤も、必要に応じて適宜に配合することができる。
In addition to the above (A), (B) and photosensitizer, for example, an acid proliferating agent can be blended in the optical photosensitive resin composition of the present invention for the purpose of further improving curability. In applications where a cured product is molded on a transparent substrate such as glass to produce an optical material, a silane or titanate cup is used to improve the adhesion between the transparent substrate and the optical material. A ring agent may be added. As other components, a flexibility imparting agent such as a synthetic rubber or a silicone compound, an antioxidant, an antifoaming agent, or the like can be blended at an appropriate ratio according to the purpose and application. Moreover, inorganic additives such as various pigments, dyes, and inorganic fillers can be appropriately blended as necessary.
本発明の光学用感光性樹脂組成物は、例えば、前記（Ａ）および（Ｂ）、さらには必要に応じてその他の添加剤を、所定の割合で配合し、加熱溶融混合することにより作製することができる。
The optical photosensitive resin composition of the present invention is prepared, for example, by blending the above-mentioned (A) and (B), and other additives as necessary, at a predetermined ratio, and heat-melt mixing. be able to.
本発明の光学用感光性樹脂組成物は、例えば、つぎのようにして使用される。すなわち、ガラス等の透明基板上に上記樹脂組成物をポッティングし、その上から所望の成形加工型を押し当てることにより、上記成形加工型内へ上記樹脂組成物を充填させ、そこへ光照射を行うことにより硬化させることができる。そして、その後、上記成形加工型を取り外すことにより、透明基板上で一体化された上記樹脂組成物の硬化体（成形加工品である光学材料）を得ることができる。あるいは、光を透過する透明型内へ樹脂組成物を充填し光硬化させることも可能である。本発明の光学用感光性樹脂組成物は、このような製法により、例えばハイブリッドレンズを作製することができる。また、本発明の光学用感光性樹脂組成物は、成形加工型内でそれ自身単独で硬化させて光学レンズ等の光学部品とすることもできる。さらに、上記光照射後の硬化体に対し、必要に応じて、所定の温度で加熱処理を行なってもよい。上記加熱により、硬化体の耐熱安定性を高めて、特に透明基板との積層物の場合には、基板と樹脂硬化物間の密着性の向上を図ることができる。
The optical photosensitive resin composition of the present invention is used, for example, as follows. That is, the resin composition is potted on a transparent substrate such as glass, and a desired molding die is pressed onto the resin composition to fill the resin composition into the molding die, and light is irradiated there. It can be cured by doing so. Then, by removing the molding die, a cured body of the resin composition integrated on the transparent substrate (an optical material that is a molded product) can be obtained. Alternatively, the resin composition can be filled into a transparent mold that transmits light and photocured. The optical photosensitive resin composition of the present invention can produce, for example, a hybrid lens by such a production method. In addition, the optical photosensitive resin composition of the present invention can be cured by itself in a molding die to be an optical component such as an optical lens. Furthermore, you may heat-process at the predetermined temperature with respect to the said hardening body after the said light irradiation as needed. By the heating, the heat resistance stability of the cured body can be improved, and particularly in the case of a laminate with a transparent substrate, the adhesion between the substrate and the cured resin can be improved.
上記光照射には、例えば、装置として紫外線（ＵＶ）ランプや特定波長のシングルバンドのランプ等を用いることができる。また、照射量としては、例えば、２０００～５００００ｍＪ／ｃｍ2が好ましく、より好ましくは２０００～３００００ｍＪ／ｃｍ2である。すなわち、照射量が上記範囲未満では、感光性樹脂組成物を充分に硬化させることが困難となり、得られる光学材料を透明基板上に所望の硬化物形状に成形することが困難となる傾向がみられる。また、上記範囲を超えると、過度の照射により光劣化が生じるという不具合が生起するおそれがあるからである。そして、照射量が上記範囲内であると、感光性樹脂組成物を充分に硬化させることができることから、例えば、感光性樹脂組成物を透明基板上に所望の硬化物形状に成形することでき、また、過度の照射による光劣化を防止することが可能となる。
For the light irradiation, for example, an ultraviolet (UV) lamp or a single band lamp having a specific wavelength can be used as an apparatus. The irradiation amount is preferably, for example, 2000 to 50000 mJ / cm 2 , more preferably 2000 to 30000 mJ / cm 2 . That is, when the irradiation amount is less than the above range, it is difficult to sufficiently cure the photosensitive resin composition, and it tends to be difficult to mold the obtained optical material into a desired cured product shape on the transparent substrate. It is done. Moreover, it is because there exists a possibility that the malfunction that photodegradation will arise by excessive irradiation may arise when it exceeds the said range. And, since the photosensitive resin composition can be sufficiently cured when the irradiation amount is within the above range, for example, the photosensitive resin composition can be molded into a desired cured product shape on a transparent substrate, Moreover, it becomes possible to prevent the light deterioration by excessive irradiation.
また、上記光照射後に必要に応じて施される加熱処理の条件としては、例えば、熱処理温度が、好ましくは５０～２００℃、より好ましくは８０～１７０℃であり、熱処理時間が、好ましくは０．５～３時間、より好ましくは０．５～２時間である。
Further, as the conditions of the heat treatment performed as necessary after the light irradiation, for example, the heat treatment temperature is preferably 50 to 200 ° C., more preferably 80 to 170 ° C., and the heat treatment time is preferably 0. .5-3 hours, more preferably 0.5-2 hours.
なお、本発明の光学用感光性樹脂組成物は、上記のような成形加工型によらず、シート状に成形することもできる。
In addition, the optical photosensitive resin composition of the present invention can be molded into a sheet shape regardless of the above-described molding die.
そして、上記のようにして得られる本発明の光学用感光性樹脂組成物は、ハンダリフローによりプリント基板等に実装することにより光学部品用成形材料（光学材料）として使用することができる。
The optical photosensitive resin composition of the present invention obtained as described above can be used as a molding material (optical material) for optical components by mounting it on a printed circuit board or the like by solder reflow.
本発明の光学用感光性樹脂組成物は、先に述べたような製法により、光学レンズ等の光学部品用の成形材料（光学材料）として用いられる他、光導波路や光学部品固定用光硬化型接着剤等、各種用途に用いることができる。
The optical photosensitive resin composition of the present invention can be used as a molding material (optical material) for optical parts such as optical lenses by the production method as described above, and is also a light curing type for fixing optical waveguides and optical parts. It can be used for various applications such as adhesives.
つぎに、本発明を実施例に基づいて説明する。ただし、本発明は、これら実施例に限定されるものではない。なお、例中、「部」とあるのは、断りのない限り重量基準を意味する。
Next, the present invention will be described based on examples. However, the present invention is not limited to these examples. In the examples, “parts” means weight basis unless otherwise specified.
まず、下記に示す各カチオン重合性化合物、光酸発生剤、シランカップリング剤を準備した。
First, each cationic polymerizable compound, photoacid generator, and silane coupling agent shown below were prepared.
＜架橋環式カチオン重合性化合物（Ａ）＞
［ａ－１］
前記式（１）で表される架橋環式炭化水素構造を有する〔式（１）中、ｍ＝１、ｎ＝２、ＸおよびＹは酸素原子〕エポキシ樹脂（ＡＤＥＫＡ社製、ＥＰ－４０８８Ｌ）
［ａ－２］
前記式（２）で表される架橋環式炭化水素構造を有する〔式（２）中、ＸおよびＹは酸素原子〕エポキシ樹脂（Ｓｙｎｑｕｅｓｔ社製、ジシクロペンタジエン ジエポキシド） <Crosslinked Cyclic Polymerizable Compound (A)>
[A-1]
Epoxy resin (made by ADEKA, EP-4088L) having a bridged cyclic hydrocarbon structure represented by the formula (1) [where m = 1, n = 2, X and Y are oxygen atoms]
[A-2]
An epoxy resin having a bridged cyclic hydrocarbon structure represented by the formula (2) [wherein X and Y are oxygen atoms] epoxy resin (manufactured by Synquest, dicyclopentadiene diepoxide)
［ａ－１］
前記式（１）で表される架橋環式炭化水素構造を有する〔式（１）中、ｍ＝１、ｎ＝２、ＸおよびＹは酸素原子〕エポキシ樹脂（ＡＤＥＫＡ社製、ＥＰ－４０８８Ｌ）
［ａ－２］
前記式（２）で表される架橋環式炭化水素構造を有する〔式（２）中、ＸおよびＹは酸素原子〕エポキシ樹脂（Ｓｙｎｑｕｅｓｔ社製、ジシクロペンタジエン ジエポキシド） <Crosslinked Cyclic Polymerizable Compound (A)>
[A-1]
Epoxy resin (made by ADEKA, EP-4088L) having a bridged cyclic hydrocarbon structure represented by the formula (1) [where m = 1, n = 2, X and Y are oxygen atoms]
[A-2]
An epoxy resin having a bridged cyclic hydrocarbon structure represented by the formula (2) [wherein X and Y are oxygen atoms] epoxy resin (manufactured by Synquest, dicyclopentadiene diepoxide)
＜カチオン重合性化合物＞
［ｃ－１］
水添ビスフェノールＡ型エポキシ樹脂（三菱化学社製、ＹＸ８０００）
［ｃ－２］
３－エチル－３｛［（３－エチルオキセタン－３－イル）メトキシ］メチル｝オキセタン（東亞合成社製、ＯＸＴ－２２１）
［ｃ－３］
２－フェニルフェノールグリシジルエーテル（三光社製、ＯＰＰ－Ｇ） <Cationically polymerizable compound>
[C-1]
Hydrogenated bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, YX8000)
[C-2]
3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (manufactured by Toagosei Co., Ltd., OXT-221)
[C-3]
2-Phenylphenol glycidyl ether (manufactured by Sanko Co., Ltd., OPP-G)
［ｃ－１］
水添ビスフェノールＡ型エポキシ樹脂（三菱化学社製、ＹＸ８０００）
［ｃ－２］
３－エチル－３｛［（３－エチルオキセタン－３－イル）メトキシ］メチル｝オキセタン（東亞合成社製、ＯＸＴ－２２１）
［ｃ－３］
２－フェニルフェノールグリシジルエーテル（三光社製、ＯＰＰ－Ｇ） <Cationically polymerizable compound>
[C-1]
Hydrogenated bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, YX8000)
[C-2]
3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (manufactured by Toagosei Co., Ltd., OXT-221)
[C-3]
2-Phenylphenol glycidyl ether (manufactured by Sanko Co., Ltd., OPP-G)
＜光酸発生剤（光重合開始剤）（Ｂ）＞
ジフェニル－４－チオフェノキシフェニルスルホニウムヘキサフルオロアンチモネートとビス〔４－（ジフェニルスルホニオ）フェニル〕スルフィド－ビス－ヘキサフルオロアンチモネートを主体とする混合物のプロピレンカーボネート５０重量％溶液（ＡＤＥＫＡ社製、ＳＰ－１７０） <Photoacid generator (photopolymerization initiator) (B)>
A 50% by weight solution of propylene carbonate (made by ADEKA, SP) -170)
ジフェニル－４－チオフェノキシフェニルスルホニウムヘキサフルオロアンチモネートとビス〔４－（ジフェニルスルホニオ）フェニル〕スルフィド－ビス－ヘキサフルオロアンチモネートを主体とする混合物のプロピレンカーボネート５０重量％溶液（ＡＤＥＫＡ社製、ＳＰ－１７０） <Photoacid generator (photopolymerization initiator) (B)>
A 50% by weight solution of propylene carbonate (made by ADEKA, SP) -170)
＜シランカップリング剤＞
トリメトキシシラングリシジルエーテル（信越化学工業社製、ＫＢＭ－４０３） <Silane coupling agent>
Trimethoxysilane glycidyl ether (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
トリメトキシシラングリシジルエーテル（信越化学工業社製、ＫＢＭ－４０３） <Silane coupling agent>
Trimethoxysilane glycidyl ether (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
〔実施例１～５、比較例１～２〕
上記各成分を、後記の表１に示す割合で配合し、加熱溶融混合を行なうことにより、光学用感光性樹脂組成物を作製した。 [Examples 1 to 5, Comparative Examples 1 and 2]
The above components were blended in the proportions shown in Table 1 below, and heated, melted and mixed to prepare an optical photosensitive resin composition.
上記各成分を、後記の表１に示す割合で配合し、加熱溶融混合を行なうことにより、光学用感光性樹脂組成物を作製した。 [Examples 1 to 5, Comparative Examples 1 and 2]
The above components were blended in the proportions shown in Table 1 below, and heated, melted and mixed to prepare an optical photosensitive resin composition.
このようにして得られた実施例および比較例の光学用感光性樹脂組成物に関し、下記の基準に従って各特性評価（屈折率、アッベ数）を行なった。その結果を、後記の表１に併せて示す。
For the optical photosensitive resin compositions of Examples and Comparative Examples thus obtained, each characteristic evaluation (refractive index, Abbe number) was performed according to the following criteria. The results are also shown in Table 1 below.
［屈折率・アッベ数］
光学用感光性樹脂組成物（液状）を、大きさ１×１．５×０．５ｃｍの透明成形型に流し込み、紫外線（ＵＶ）を３００００ｍＪ／ｃｍ2照射し硬化させた後、成形型から取り出し、さらに１５０℃×１時間の加熱処理を行なうことにより光学材料（硬化体）を作製した。このようにして得られた光学材料の表面を、グラインダーを用いて研磨した後、屈折率計（アタゴ社製）を用いて、２５℃環境下でのナトリウムｄ線での光学材料の屈折率を測定した。また、同時に測定波長をナトリウムｃ線およびｆ線とし、これらの場合における屈折率の測定値よりアッベ数を求めた。 [Refractive index / Abbe number]
An optical photosensitive resin composition (liquid) is poured into a transparent mold having a size of 1 × 1.5 × 0.5 cm, cured by irradiation with ultraviolet rays (UV) at 30000 mJ / cm 2 , and then taken out from the mold. Further, an optical material (cured body) was produced by performing a heat treatment at 150 ° C. for 1 hour. After polishing the surface of the optical material thus obtained using a grinder, the refractive index of the optical material at the sodium d line in a 25 ° C. environment is measured using a refractometer (manufactured by Atago Co., Ltd.). It was measured. At the same time, the measurement wavelength was set to sodium c-line and f-line, and the Abbe number was obtained from the measured values of refractive index in these cases.
光学用感光性樹脂組成物（液状）を、大きさ１×１．５×０．５ｃｍの透明成形型に流し込み、紫外線（ＵＶ）を３００００ｍＪ／ｃｍ2照射し硬化させた後、成形型から取り出し、さらに１５０℃×１時間の加熱処理を行なうことにより光学材料（硬化体）を作製した。このようにして得られた光学材料の表面を、グラインダーを用いて研磨した後、屈折率計（アタゴ社製）を用いて、２５℃環境下でのナトリウムｄ線での光学材料の屈折率を測定した。また、同時に測定波長をナトリウムｃ線およびｆ線とし、これらの場合における屈折率の測定値よりアッベ数を求めた。 [Refractive index / Abbe number]
An optical photosensitive resin composition (liquid) is poured into a transparent mold having a size of 1 × 1.5 × 0.5 cm, cured by irradiation with ultraviolet rays (UV) at 30000 mJ / cm 2 , and then taken out from the mold. Further, an optical material (cured body) was produced by performing a heat treatment at 150 ° C. for 1 hour. After polishing the surface of the optical material thus obtained using a grinder, the refractive index of the optical material at the sodium d line in a 25 ° C. environment is measured using a refractometer (manufactured by Atago Co., Ltd.). It was measured. At the same time, the measurement wavelength was set to sodium c-line and f-line, and the Abbe number was obtained from the measured values of refractive index in these cases.
上記結果から、架橋環式炭化水素構造を有するカチオン重合性化合物を用いた実施例品は、高い屈折率を示すとともに、高アッベ数を有するものであった。従って、実施例品の光学用感光性樹脂組成物の使用により、高屈折率および高アッベ数を備えた光学レンズ等の光学材料を提供することが可能となる。
From the above results, the example product using the cationic polymerizable compound having a crosslinked cyclic hydrocarbon structure showed a high refractive index and a high Abbe number. Therefore, it is possible to provide an optical material such as an optical lens having a high refractive index and a high Abbe number by using the optical photosensitive resin composition of the example product.
これに対して、比較例品は、従来のカチオン重合性化合物を用いた態様であり、屈折率およびアッベ数の双方ともに実施例品に比べて低いものであった。
On the other hand, the comparative example product was an embodiment using a conventional cationic polymerizable compound, and both the refractive index and the Abbe number were lower than those of the example product.
上記実施例においては、本発明における具体的な形態について示したが、上記実施例は単なる例示にすぎず、限定的に解釈されるものではない。当業者に明らかな様々な変形は、本発明の範囲内であることが企図されている。
In the above embodiments, specific forms in the present invention have been described. However, the above embodiments are merely examples and are not construed as limiting. Various modifications apparent to those skilled in the art are contemplated to be within the scope of this invention.
本発明の光学用感光性樹脂組成物は、高い透明性を有しながら、高屈折率および高アッベ数を有する立体造形物（硬化物）となり得るため、光学レンズ等の光学部品用の成形材料（光学材料）や、光学部品固定用光硬化型接着剤等の光学用途として有用である。また、本発明の光学用感光性樹脂組成物を用いた光学材料は、信頼性が高いため、光学レンズ等の光学製品に用いることができる。
The optical photosensitive resin composition of the present invention can be a three-dimensionally shaped product (cured product) having a high refractive index and a high Abbe number while having high transparency. Therefore, it is a molding material for optical components such as optical lenses. It is useful for optical applications such as (optical material) and a photo-curing adhesive for fixing optical components. Moreover, since the optical material using the optical photosensitive resin composition of the present invention has high reliability, it can be used for optical products such as optical lenses.
Claims (7)
- 下記の（Ａ）および（Ｂ）を含有することを特徴とする光学用感光性樹脂組成物。
（Ａ）架橋環式炭化水素構造を有するカチオン重合性化合物。
（Ｂ）光酸発生剤。 An optical photosensitive resin composition comprising the following (A) and (B):
(A) A cationically polymerizable compound having a crosslinked cyclic hydrocarbon structure.
(B) A photoacid generator. - 架橋環式炭化水素構造の架橋環構造が、シクロペンタン構造を有する請求項１記載の光学用感光性樹脂組成物。 The optical photosensitive resin composition according to claim 1, wherein the crosslinked ring structure of the crosslinked cyclic hydrocarbon structure has a cyclopentane structure.
- 架橋環式炭化水素構造の架橋環構造が、ジシクロペンタン構造を有する請求項１または２記載の光学用感光性樹脂組成物。 The photosensitive resin composition for optical use according to claim 1 or 2, wherein the crosslinked ring structure of the crosslinked cyclic hydrocarbon structure has a dicyclopentane structure.
- カチオン重合性化合物（Ａ）が、下記の一般式（１）で表される架橋環構造を有するカチオン重合性化合物、および、下記の一般式（２）で表される架橋環構造を有するカチオン重合性化合物の少なくとも一方である請求項１～３のいずれか一項に記載の光学用感光性樹脂組成物。
- （Ａ）架橋環式炭化水素構造を有するカチオン重合性化合物が、架橋環式炭化水素構造を有するエポキシ化合物である請求項１～４のいずれか一項に記載の光学用感光性樹脂組成物。 5. The optical photosensitive resin composition according to claim 1, wherein the cationic polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure is an epoxy compound having a crosslinked cyclic hydrocarbon structure.
- カチオン重合性化合物成分として、架橋環式炭化水素構造を有するカチオン重合性化合物（Ａ）とともに、架橋環式炭化水素構造を有さないカチオン重合性化合物を含有する請求項１～５のいずれか一項に記載の光学用感光性樹脂組成物。 The cation polymerizable compound component contains a cation polymerizable compound (A) having a crosslinked cyclic hydrocarbon structure and a cation polymerizable compound not having a crosslinked cyclic hydrocarbon structure as a cationic polymerizable compound component. The photosensitive resin composition for optics as described in an item.
- 請求項１～６のいずれか一項に記載の光学用感光性樹脂組成物を硬化させることにより得られてなる光学材料。 An optical material obtained by curing the optical photosensitive resin composition according to any one of claims 1 to 6.
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| JP2014175130A JP2016050230A (en) | 2014-08-29 | 2014-08-29 | Photosensitive resin composition for optical use and optical material using the same |
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| TWI764921B (en) * | 2016-08-31 | 2022-05-21 | 日商東京應化工業股份有限公司 | Negative photosensitive resin composition, photosensitive resist film, pattern formation method, curing film and producing method for curing film |
| WO2023132249A1 (en) * | 2022-01-04 | 2023-07-13 | 三井化学株式会社 | Resin composition for lens, cured product for lens, and lens |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| JP2003261648A (en) * | 2002-03-12 | 2003-09-19 | Mitsubishi Chemicals Corp | Heterocycle-containing compound and composition containing this |
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| TWI764921B (en) * | 2016-08-31 | 2022-05-21 | 日商東京應化工業股份有限公司 | Negative photosensitive resin composition, photosensitive resist film, pattern formation method, curing film and producing method for curing film |
| US11415888B2 (en) | 2016-08-31 | 2022-08-16 | Tokyo Ohka Kogyo Co., Ltd. | Negative type photosensitive resin composition, photosensitive resist film, pattern forming method, cured film, and method of producing cured film |
| WO2023132249A1 (en) * | 2022-01-04 | 2023-07-13 | 三井化学株式会社 | Resin composition for lens, cured product for lens, and lens |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016050230A (en) | 2016-04-11 |
| TW201612628A (en) | 2016-04-01 |
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