JP6507683B2 - Resin composition and optical member - Google Patents

Description

  The present disclosure relates to a resin composition and an optical component using the same.

  In recent years, instead of inorganic glass, information terminals such as mobile phones, flat panel displays, lens materials, optical fibers, etc. are lighter, have high impact resistance, and organic such as plastics with high production efficiency Materials are becoming widely used.

  Above all, materials used in the manufacturing field of members requiring high refractive index are required to have a low degree of difference in refractive index depending on wavelength as well as high refractive index (high Abbe number) . However, in the case of organic materials such as plastics, the refractive index and the Abbe number are in a contradictory relationship, and it has been difficult to simultaneously satisfy both of them simultaneously.

  In view of the problems with such materials, improvements have been made, and materials have been proposed which have both a high refractive index and a high Abbe number. For example, Patent Document 1 uses a polymer material obtained by Michael addition polymerization of 1,4-dithiane-2,5-dithiol and divinyl sulfone, and Patent Document 2 discloses 2,5. The use of a polymerization reaction of bis (mercaptomethyl) -1,4-dithiane with divinylsulfone or bis (vinylsulfone) methane has been studied.

  Furthermore, in recent years, hybrid materials in which an organic material and an inorganic material are complexed at the molecular level have been studied. Specifically, metal oxide nanoparticles [titanium oxide (refractive index: 2.5-2.7), zirconium oxide (refractive index: 2.] for the purpose of imparting high refractive index, mechanical strength and the like to organic materials 1-2.2), a hybrid material in which barium titanate (refractive index: 2.4) is dispersed to be transparent has been studied. For example, in patent document 3, using a resin composition containing zirconium oxide and an acrylic resin to improve the refractive index and the Abbe number is examined.

JP, 2009-209277, A JP, 2010-84122, A International Publication No. 2007/032217

  On the other hand, in the field of manufacturing lens materials and the like, it is required that a lens material or the like having a thick film can be manufactured using a transparent material capable of achieving both a high refractive index and a high Abbe number. However, when a thick film having a thickness of 50 μm or more is formed using the material described in Patent Document 3, the transmittance may be reduced. Therefore, there is an urgent need to develop a transparent material that has both a high refractive index and a high Abbe number and can maintain the transmittance.

  The present disclosure has been made in view of the above problems, and provides a resin composition which can maintain transparency and is excellent in refractive index and Abbe number even when a thick film having a thickness of 50 μm or more is formed. The purpose is

  The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, (A) component: a compound having a fluorene skeleton, (B) component: a polymerizable compound having an aromatic ring, and (C) component: photopolymerization By using a resin composition containing an initiator, even when a thick film having a thickness of 50 μm or more is formed, transparency can be maintained, and a resin composition excellent in refractive index and Abbe number can be provided. I found it.

  The component (B) may contain two or more aromatic rings. This can further increase the refractive index.

  Moreover, the resin composition of this embodiment may further contain (D) component: an inorganic compound, and may contain a zirconium oxide as said inorganic compound. Thereby, the refractive index and the Abbe number can be further improved. The average particle diameter of the component (D) may be 50 nm or less, and the component (D) may have a functional group capable of reacting with the (meth) acryloyl group. Thereby, even if content of an inorganic compound increases, the fall of the transmittance | permeability can be suppressed. In addition, the component (D) may be surface-treated, whereby higher transmittance and high resin strength can be obtained.

  Furthermore, the optical member provided with the transparent material which is excellent in a refractive index and an Abbe's number can be provided by using the resin composition of this embodiment.

  According to the present disclosure, even when a thick film having a thickness of 50 μm or more is formed, it is possible to provide a resin composition which can maintain transparency and is excellent in refractive index and Abbe number. Therefore, it can be suitably used as an optical material.

  Hereinafter, preferred embodiments of the present disclosure will be described, but the present disclosure is not limited to these embodiments. In the present specification, "(meth) acrylic" means "acrylic" or "methacrylic" corresponding thereto. The same applies to other similar expressions such as (meth) acryloyl. Moreover, (meth) acrylic acid ester may be described as (meth) acrylate.

  The resin composition of the present embodiment contains (A) component: a compound having a fluorene skeleton, (B) component: a polymerizable compound having an aromatic ring, and (C) component: a photopolymerization initiator. In addition, in this specification, these components may only be called (A) component, (B) component, (C) component etc. The component (A) can also be said to be a compound having a fluorene-derived skeleton. The fluorene skeleton can also be said to be a 9,9-bisphenylfluorene skeleton.

  The resin composition of the present embodiment can be suitably used for lens formation applications, exhibits high refractive index and low wavelength dispersion (high Abbe number), and has high transparency even in a thick film.

<Compound Having a Fluorene Skeleton>
Component (A): The compound having a fluorene skeleton (hereinafter sometimes simply referred to as a fluorene compound) may be a compound represented by the following general formula (1).

（一般式（１）中、Ｒ¹〜Ｒ⁴は、非反応性基又は反応性基を示す。ｋ１及びｋ２は１〜５の整数を示し、ｍ１及びｍ２は０又は１〜４の整数を示す。なお、Ｒ¹〜Ｒ⁴と、ｋ１及びｋ２と、ｍ１及びｍ２とは、お互いに同一であってもよく、異なっていてもよい。）

(In the general formula (1), R ^{1 to} R ^{4 each} represent a non-reactive group or a reactive group. K 1 and k 2 each represent an integer of 1 to 5; m 1 and m 2 each represent an integer of 0 or 1 to 4) In addition, R ^{1 to} R ⁴ , k1 and k2, and m1 and m2 may be identical to or different from each other.)

  The non-reactive group is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group; a halogen atom (a fluorine atom, a chlorine atom and the like), a nitro group and a cyano group.

Examples of the reactive group include a group containing active hydrogen (active hydrogen-containing group) and a group obtained through the active hydrogen-containing group. As an active hydrogen-containing group, for example, a hydroxyl group, an amino group, an N-monosubstituted amino group [eg, an amino group substituted with a hydrocarbon group (N-mono C _1-6 alkylamino group such as a methylamino group)] ], A carboxyl group is mentioned, Usually, they are a hydroxyl group, an amino group, or N-mono substituted amino group (especially hydroxyl group, amino group).

Examples of the group obtained through the active hydrogen-containing group include groups obtained through the active hydrogen of the active hydrogen-containing group (in particular, a hydroxyl group and an amino group). Such a group is not particularly limited, but a group obtained through the active hydrogen of a hydroxyl group or an amino group, for example, a group-[X- (R ⁵ O) _n -Y] (wherein R ⁵ is alkylene A group X, an oxygen atom (ether group) or an imino group, a group Y a hydrogen atom, a glycidyl group or a (meth) acryloyl group, and n represents an integer of 0 or 1 or more, When n is 0, Y is not a hydrogen atom.

The alkylene group represented by the group R ⁵ is not particularly limited, and examples thereof include a C _2-4 alkylene group (ethylene group, trimethylene group, propylene group, butane-1,2-diyl group, etc.), and in particular, And C _2-3 alkylene groups (in particular, ethylene and propylene groups) are preferable. R ⁵ may be the same or different alkylene groups in the corresponding active hydrogen-containing groups R ¹ (or R ² ), but is usually the same.

  The substitution number (or addition number) n of the alkyleneoxy unit may be the same or different and may be selected from the range of 0 or 1 to 15, for example, 0 or 1 to 12, preferably 0 or 1 to 8, more preferably It may be about 0 or 1 to 6, particularly 0 or 1 to 4. When n is 2 or more, the polyalkoxy group (polyalkyleneoxy group) may be composed of the same alkylene group, and different alkylene groups (for example, ethylene group and propylene group) are mixed and configured Although it may be, it is usually composed of the same alkylene group in many cases.

The groups R ¹ and R ² are usually at least often reactive groups. For example, when k1 and k2 are 2, one or two of the two groups R ¹ is a reactive group, and one or two of the two groups R ² is a reactive group.

Preferred groups R ¹ (or R ² ) include alkyl groups (C _1-6 alkyl groups), cycloalkyl groups (C _5-8 cycloalkyl groups), aryl groups (C _6-10 aryl groups) and aralkyl groups (C _6-10 aryl groups) C _6-8 aryl-C _1-2 alkyl group), alkoxy group (C _1-4 alkoxy group), hydroxyl group, amino group, N-monosubstituted amino group (N-C _1-4 alkylamino group), group - include _{^{[X- (R 5 O) n}} -Y]. In particular, the alkyl group (C _1-4 alkyl group), the aryl group (C _6-8 aryl group), the aralkyl group (C _6-8 aryl-C _1-2 alkyl group), the hydroxyl group, the amino group, [X- (R ⁵ O) _n -Y], and the groups R ¹ and R ² include at least a hydroxyl group, an amino group, or the group-[X- (R ⁵ O) _n -Y] Is preferred. The groups R ¹ (or R ² ) may be substituted on the benzene ring singly or in combination of two or more. Also, the radicals R ¹ and R ² may be identical or different from one another, but are usually identical. Furthermore, the groups R ¹ (or R ² ) may be different or identical in the same benzene ring.

Incidentally, the substitution position of group R ¹ (or R ²⁾ is not particularly limited, may be selected from 2 to 6-position of the phenyl group substituted at position 9 of the fluorene. Usually, the 4-position of a phenyl group (ie, phenyl group) in which one reactive group (hydroxyl group, amino group, the group-[X- (R ⁵ O) _n -Y], etc., is substituted at the 9-position of fluorene May be substituted to 4).

Preferred substitution numbers k1 and k2 are 1 to 4, more preferably 1 to 3 (especially 1 to 2). Also, the number of reactive groups is preferably 1 to 3, and more preferably 1 to ² in each of the groups R ¹ and R ² . The substitution numbers k1 and k2 may be different, but usually, they are often the same.

Also, the groups R ³ and R ⁴ are usually alkyl groups (C _1-4 alkyl groups, in particular methyl groups). The radicals R ³ and R ⁴ may be different from one another or identical. The groups R ³ (or R ⁴ ) may be different or the same in the same benzene ring. The bonding position (substituting position) of the group R ³ (or R ⁴ ) to the benzene ring constituting the fluorene skeleton is not particularly limited. The preferred substitution numbers m1 and m2 are 0 or 1, more preferably 0. The substitution numbers m1 and m2 may be different but are usually the same.

  Specific fluorene compounds include, for example, 9,9-bis (hydroxyphenyl) fluorenes. Among them, fluorene compounds having a (meth) acrylate capable of photopolymerization as a reactive group are preferable.

((Meth) acrylate)
As the (meth) acrylate of representative 9,9-bis (hydroxyphenyl) fluorenes, a compound in which glycidyl group of glycidyl ether is substituted with (meth) acryloyl group, for example, 9,9-bis ((meth) acryloyl) Oxyphenyl) fluorene [eg, 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene], 9,9-bis ((meth) acryloyloxyphenyl) fluorene having a substituent {eg, 9,9- Bis (alkyl- (meth) acryloyloxyphenyl) fluorene [eg, 9,9-bis (C _1-4 alkyl-4) such as 9,9-bis (3-methyl-4- (meth) acryloyloxyphenyl) fluorene 9,9-bis (monohydroxy) such as-(meth) acryloyloxyphenyl) fluorene]} Di (meth) acrylates of phenyl) fluorenes; (meth) acrylates of 9,9-bis [di or tri (hydroxy) phenyl] fluorenes corresponding to these compounds {eg, 9,9-bis (di (meth) acrylates 9,9-bis (dihydroxyphenyl) fluorene tetra (meth) acrylates} such as acryloyloxyphenyl) fluorene [9,9-bis (3,4-di (meth) acryloyloxyphenyl) fluorene] and the like. .

Further, examples of (meth) acrylates of alkylene oxide adducts of 9,9-bis (hydroxyphenyl) fluorenes include, for example, 9,9-bis ((meth) acryloyloxy C _2-4 alkoxy) phenyl) fluorene [eg, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) fluorene], 9,9-bis ((meth) acryloyloxy C _2-4 alkoxy) phenyl) fluorene having a substituent [eg, 9,9-Bis (alkyl- (meth) acryloyloxy C _2-4 alkoxy) phenyl) fluorene such as 9,9-bis (3-methyl-4- (2- (meth) acryloyloxyethoxy) phenyl) fluorene 9, 9-bis ((meth) acryloyloxypolyC _2-4 alkoxyphenyl) corresponding to these compounds The di (meth) ene of alkylene oxide adducts of 9,9-bis (monohydroxyphenyl) fluorenes such as fluorene [eg, 9,9-bis (4- (2- (meth) acryloyloxydiethoxy) phenyl) fluorene]. Acrylate; (meth) acrylates of alkylene oxide adducts of 9,9-bis [di or tri (hydroxy) phenyl] fluorenes corresponding to these compounds {eg, 9,9-bis [3,4-di ( 9,9-Bis [di (2- (meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorene such as 2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis {3,4-di 9,9-bis {di [2- (2) such as [2- (2- (meth) acryloyloxyethoxy) ethoxy] phenyl} fluorene Tetra (meth) acrylates of alkylene oxide adducts of 9,9-bis [di (hydroxy) phenyl] fluorenes such as-(meth) acryloyloxy C _2-4 alkoxy) C _2-4 alkoxy] phenyl} fluorene It can be illustrated.

  Since the resin composition of the present embodiment contains a compound having a fluorene skeleton, there is no need to introduce the fluorene skeleton by a complicated polymerization reaction, and an effect (for example, high refractive index) excellent easily and efficiently It can be applied to the composition and its cured product. Moreover, when using the (meth) acrylate of fluorenes, since it has a photopolymerizable group, it becomes possible to harden | cure in a short time by photocuring.

<Polymerizable Compound Having an Aromatic Ring>
The resin composition according to the present embodiment can be designed as a photocurable system by using a polymerizable compound having an aromatic ring as the component (B): a resin composition having high transparency and high refractive index It is possible to apply to

  The polymerizable compound having an aromatic ring refers to a compound having one or more aromatic rings and one or more polymerizable groups. From the viewpoint of increasing the refractive index, it is preferable to have two or more aromatic rings. The polymerizable group may be, for example, at least one selected from the group consisting of (meth) acryloyl group, vinyl group, allyl group, epoxy group, and oxetanyl group. Among these functional groups, a (meth) acryloyl group is preferable in order to further shorten the curing time and to realize high throughput. The number of photopolymerizable functional groups is not particularly limited.

  As a polymerizable compound having an aromatic ring, for example, bisphenol A EO modified di (meth) acrylate, bisphenol A PO modified di (meth) acrylate, benzyl (meth) acrylate, phenoxy (di) ethyl (meth) acrylate, Nonylphenol ethylene oxide modified acrylate, O-phenylphenol EO modified acrylate are mentioned. Among them, from the viewpoint of improving the refractive index, it is preferable to include a compound having two or more aromatics, and it is preferable to include an O-phenylphenol EO-modified acrylate. In addition, "O-" means an "ortho" position.

<Photoinitiator>
The resin composition according to the present embodiment can be designed as a photo-curing system by using the component (C): photopolymerization initiator, and for example, shortening of the curing time can be achieved by adopting an exposure step. It is possible to

  Examples of the photopolymerization initiator include acyl phosphine oxides, oxime esters, aromatic ketones, quinones, benzoin ether compounds, benzyl derivatives, 2,4,5-triarylimidazole dimers, acridine derivatives and coumarins. The compounds include N-phenylglycine derivatives. In addition, the photoinitiator used by this embodiment may be synthesize | combined by a conventional method, and a commercially available thing may be obtained.

  Among these, acyl phosphine oxides, oxime esters, or aromatic ketones are preferable from the viewpoint of improvement in photocurability and sensitization and further excellent transparency of a cured film.

  In addition, a photoinitiator can be used individually by 1 type or in combination of 2 or more types.

(Acyl phosphine oxide)
As the acyl phosphine oxide, for example, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide (commercially available product: “IRGACURE-819” (manufactured by BASF (“IRGACURE” is a registered trademark))), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available product: “LUCIRIN TPO” (manufactured by BASF (“LUCIRIN” is a registered trademark))).

(Oxime esters)
Examples of oxime esters include 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyloxime) (commercially available product: “IRGACURE-OXE01” (manufactured by BASF)), 1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (commercially available: "IRGACURE-OXE 02" (manufactured by BASF)), 1 -Phenyl-1,2-propanedione-2- [o- (ethoxycarbonyl) oxime] (commercially available product: "Quantacure-PDO" (manufactured by Nippon Kayaku Co., Ltd.)).

(Aromatic ketone)
Examples of the aromatic ketone include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4 ' -Dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available: "IRGACURE-651" (manufactured by BASF)), 2-benzyl-2-dimethylamino-1- (4) -Morpholinophenyl) -butan-1-one (commercially available: "IRGACURE-369" (manufactured by BASF)), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one ON (commercially available product: “IRGACURE-907” (manufactured by BASF)), 2-hydroxy-1- {4- [4- (2-hydro) Xyl-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (commercially available: “IRGACURE-127” (manufactured by BASF)), 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available Product: "IRGACURE-184" (made by BASF Corporation) is mentioned.

<Inorganic compounds>
The resin composition according to the present embodiment can further improve the refractive index and the Abbe number by using the component (D): an inorganic compound.

  Examples of the inorganic compound include zirconia oxide, titanium oxide, zinc oxide, tungsten oxide, alumina, silica and titanium oxide, and zirconium oxide is preferable from the viewpoint of further excellent refractive index. From the viewpoint of further improving the transmittance, the average particle diameter of the inorganic compound is preferably 100 nm or less, and more preferably 50 nm or less in order to further improve the transmittance even if it is a thick film having a thickness of 50 μm or more. In particular, when the average particle size is 20 nm or less, the influence of Rayleigh scattering is very small, and the transmittance of the resin composition can be kept high, which is more preferable.

  In addition, the measurement of the average particle diameter of (D) component is performed by the laser diffraction and scattering method. The measurement of the average particle diameter of the component (D) by the laser diffraction / scattering method is performed as follows. First, the component (D) is added to the solvent (methyl ethyl ketone) in the range of 0.01 to 0.1% by mass. The additive is dispersed by vibrating this solvent with a 50 W ultrasonic homogenizer for 15 to 30 minutes, and about 5 mL of the solution is injected into the cell and measured at 25 ° C. This measurement is performed using a laser diffraction / scattering type nanoparticle size distribution measuring device SALD-7500 nano (manufactured by Shimadzu Corporation, trade name ("SALD" is a registered trademark)), with a refractive index of 1.3 and an absorption of 0. Measure the distribution. And let the particle size in 50% of integration value (volume basis) in this particle size distribution be an average particle diameter.

  From the viewpoint of further improving the transparency even with a thick film having a thickness of 50 μm or more, it is preferably an inorganic compound which is surface-treated. In particular, inorganic compounds surface-treated with a polymerizable compound are more preferable, and zirconium oxide surface-treated with a polymerizable compound is more preferable. By containing zirconium oxide surface-treated with a polymerizable compound, it can be easily reacted with the photocurable resin compound of the present embodiment to realize a higher transmittance and to increase the strength of the entire resin. it can. In addition, the inorganic compound can have a functional group which can react with a (meth) acryloyl group by surface-treating the inorganic compound with a polymerizable compound. That is, since it can react with at least one of the component (A) and the component (B), the transparency can be improved, and the refractive index and the Abbe's number can be improved. The functional group capable of reacting with the (meth) acryloyl group may be at least one selected from the group consisting of (meth) acryloyl group, vinyl group, allyl group, epoxy group, and oxetanyl group, and (meth) acryloyl group may be used. It may be a group or a vinyl group.

  In the embodiment, the content of the component (A) is 1 to 80 from the viewpoint of further improving the viscosity and the moldability of the entire resin compound with respect to the total amount of 100 parts by mass of the component (A) and the component (B). The amount is preferably in the range of 50 to 80 parts by mass from the viewpoint of further improving the refractive index. Accordingly, the content of the component (B) is preferably 20 to 99 parts by mass and 20 to 50 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). Is more preferred.

  The content of the component (C) is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, still more preferably 100 parts by mass of the total of the components (A) and (B). Is 0.1 to 2 parts by mass. By the said content being the said range, foaming, turbidity, coloring, and a crack of hardened | cured material can be reduced.

  The content of the component (D) is preferably 5 to 700 parts by mass with respect to the total amount of 100 parts by mass of the components (A) and (B), and the formability and film of the film formed using the resin composition From the viewpoint of further improving the strength, it is more preferably 5 to 500 parts by mass, and from the viewpoint of further improving the refractive index and the Abbe number, it is more preferably 100 to 400 parts by mass.

  From the viewpoint of further improving heat resistance, the resin composition according to the present embodiment may further contain (E) component: an antioxidant. Although there is no restriction | limiting in particular as (E) component, It is preferable to mix | blend the compound (henceforth "hindered phenol type compound") which has a hindered phenol type structure.

  In addition, as a hindered phenol type compound which can be used by this embodiment, the compound which has at least one group (hindered phenol group) represented by following General formula (2) in 1 molecule is mentioned.

（一般式（２）中、Ｒ_７及びＲ_８はそれぞれ独立に、水素、直鎖状アルキル基又は分岐鎖状アルキル基を示す。なお、直鎖状アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基が挙げられる。分岐鎖状アルキル基としては、例えば、イソプロピル基、イソブチル基、ｔ−ブチル基が挙げられる。１分子中に一般式（２）で表される基が複数あるとき、Ｒ_７及びＲ_８は、複数の基において、同一であっても異なっていてもよい。また、上記一般式（２）中の芳香族環において、フェノール基、Ｒ_７及びＲ_８以外に、低級アルキル基等の基を有していてもよい。）

(In the general formula (2), R ₇ and R ₈ each independently represent hydrogen, a linear alkyl group or a branched alkyl group. Examples of the linear alkyl group include a methyl group and an ethyl group. Examples of the branched alkyl group include an isopropyl group, an isobutyl group and a t-butyl group, and a group represented by General Formula (2) in one molecule. When there are plural R _{7 s} and R _{8 s} may be the same or different in a plurality of groups, and in the aromatic ring in the above general formula (2), a phenol group, R _{7 s} and R _{8 s} Other than these, it may have a group such as a lower alkyl group etc.)

As the hindered phenol compound which can be used in the present embodiment, a compound in which R ₇ and / or R _{8 in the} general formula (2) is a branched alkyl group is preferable, and at least one of R ₇ and R ₈ is preferable. Compounds in which one is a t-butyl group are more preferable, and compounds in which both R ₇ and R ₈ are a t-butyl group are more preferable.

  Such hindered phenolic compounds may be synthesized by conventional methods or may be commercially available. In addition, these antioxidants can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (E) is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, further preferably 100 parts by mass of the total of the components (A) and (B). Is 0.1 to 3 parts by mass. The resin coloring in high temperature can be suppressed because the said content is the said range.

  The resin composition according to the present embodiment may further contain a (F) component: a thermal polymerization initiator. By using the component (F) in combination with the component (C), it becomes possible to design not only as a photo-curing system but also as a thermosetting system. For example, even a thick film sample is sufficiently It can be cured.

  As the component (F), for example, dilauroyl peroxide (commercially available product: “Paroyl L” (manufactured by NOF Corporation (“Paroyl” is a registered trademark)), 1,1,3,3-trimethylbutylperoxy- 2-ethylhexanate (commercially available product: "Perocta O" (manufactured by NOF Corporation ("Perocta" is a registered trademark)), benzoyl peroxide (commercially available: "Nyper BW" (manufactured by NOF Corporation, "Nyper Is a registered trademark))), 1,1-di (t-hexylperoxy) cyclohexane (commercially available product: “Perhexa HC” (manufactured by NOF Corporation (“Perhexa” is a registered trademark))), t-butyl Cumyl peroxide (commercially available product: “Perbutyl C” (manufactured by NOF Corporation (“Perbutyl” is a registered trademark)), n-butyl 4, 4-di- (t-butylperoxy) valerate Commercially available products: Peroxides such as "Perhexa V" (manufactured by NOF Corporation), Dicumyl peroxide (commercial products: "PARK MIL D" (manufactured by NOF Corporation ("PARK MIL" is a registered trademark)) Can be mentioned. In addition, a thermal radical polymerization initiator can be used, and the thermal radical polymerization initiator is not particularly limited as long as it generates free radicals by heating.

  In addition, (F) component can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (F) is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, further preferably 100 parts by mass of the total of the components (A) and (B). Is 0.5 to 3 parts by mass.

(Light curing method)
The resin composition of the present embodiment can obtain a cured product by light curing. The type of light to be irradiated is not particularly limited, and for example, at least one type of actinic light selected from the group consisting of ultraviolet light, visible light, electron beam and X-ray is irradiated using a light source commonly used in the art. Ru. Among these, ultraviolet light and visible light are particularly preferable. The exposure dose is, for example, 1 to 4000 mJ / cm ² , preferably 1 to 2000 mJ / cm ² . When the solvent is contained, the solvent may be removed by using a heating device such as an oven or a hot plate before and after the light curing.

(Pattern formation method)
Although the method to form a pattern using the resin composition of this embodiment is not specifically limited, A well-known heat / light imprint method can be used.

<Optical parts>
The optical component according to the present embodiment includes a resin layer (cured film) having a pattern formed by the above-described method as a permanent film. The type of the optical component of the present embodiment is not particularly limited. In particular, it can be suitably used as an optical component utilizing the excellent optical properties of the cured resin composition, particularly as an optical component that transmits light (so-called passive optical component). As an optical functional device provided with such an optical component, for example, resin (sealing agent, adhesive agent) for optical semiconductor (LED etc.), flat panel display (organic EL element etc.), electronic circuit, optical circuit (optical waveguide) (Cladding / core material), lenses for optical communication, and optical electronic members such as optical films. In particular, it is suitable for a sealing agent for semiconductor light emitting devices (LED etc.), an optical lens, an adhesive for optics, a sealing agent for optics, and an optical waveguide.

  The "permanent film" is a film that constitutes an optical component or the like as a finished product without being removed in the process of manufacturing the optical component or the like. The optical component according to the present embodiment only needs to have the permanent film formed by the method according to the present embodiment, and the structure and the like thereof are not particularly limited.

Hereinafter, although the purpose and advantage of the present disclosure will be more specifically described based on examples , reference examples, and comparative examples, the present disclosure is not limited to the following examples. That is, it should be construed that the specific disclosure and the amount thereof and other conditions and details listed in these examples do not unduly limit the present disclosure.

(A) component, (B) component, (C) component, (D) component and other components are mixed with the blending ratio (parts by mass, solid content ratio) shown in Table 1, Reference Examples 1 to 2, The resin compositions of Examples 3 to 4 and Reference Example 3 and Comparative Example 1 were obtained. Each component in Table 1 is shown below.

<(A) component>
・ GA-5000 (fluorene-based epoxy acrylate, manufactured by Osaka Gas Chemical Co., Ltd., trade name) (Diluted with methyl isobutyl ketone (MIBK), 71% by mass of NV (nonvolatile matter))
<(B) component>
・ FA-301A (orthophenyl phenoxyethyl acrylate, manufactured by Hitachi Chemical Co., Ltd., trade name)
・ 702A (2-hydroxy-3-phenoxypropyl acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name)
<Comparative component of (B) component>
・ FA-513AS (dicyclopentanyl acrylate, manufactured by Hitachi Chemical Co., Ltd., trade name)
<(C) component>
-I-184 (1-hydroxycyclohexyl phenyl ketone, manufactured by BASF, trade name "Irgacure-184")
<(D) Inorganic compound>
・ OZ-S40K-AC (zirconium oxide, manufactured by Nissan Chemical Industries, Ltd., trade name, average particle diameter: 15 nm) (diluted with methyl ethyl ketone (MEK) solvent, NV 40 mass%) It has a functional group that can react with the group.)

<Preparation of evaluation sample>
The resin compositions of Examples , Reference Examples and Comparative Examples were applied on a substrate using an applicator so as to make the thickness uniform, and left in an oven at a temperature of 100 ° C. for 10 minutes. After that, using a high-precision parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd.), light irradiation is performed under a nitrogen atmosphere at an exposure amount of 4000 mJ / cm ² to obtain resin layers having thicknesses shown in Table 2 for evaluation. It was a sample.

<Measurement of thickness and transmittance>
After measuring the thickness of the sample for evaluation with a film thickness meter, the sample for evaluation is laminated on glass on a hot plate, and the transmittance of this test substrate is used as a reference for the transmittance of glass alone as a UV-visible spectrophotometer The light transmittance at a wavelength of 400 nm was measured using (product name: “U-3310 Spectrophotometer” (manufactured by Hitachi High-Tech Co., Ltd.)) and used as the transmittance. The results are shown in Table 2.

<Measurement of refractive index and Abbe number>
The sample for evaluation was cut into a rectangle of 1 cm long and 2 cm wide, and used as a sample for refractive index and Abbe number measurement. The refractive index of D line (589 nm), F line (486 nm), and C line (656 nm) was measured using multi-wavelength Abbe refractometer DR-M4 (product name, manufactured by Atago Co., Ltd.) to calculate Abbe number. In addition, the refractive index was evaluated by the value with respect to D line. Also, each time of measurement, calibration was performed using pure water. The results are shown in Table 2.

From the results of Table 2, in the reference examples 1 and 5 containing the components (A), (B) and (C), the refractive index is 1.6 or more, and a high refractive index of 1.6 or more can be obtained. I found that.

Moreover, in the reference example 2 and Examples 3 to 4 in which the resin composition containing the (A) component, the (B) component and the (C) component further contains the (D) component, the oxidation which is the (D) component It was found that as the content of zirconia was increased, both the refractive index and the Abbe's number increased, and the refractive index and the Abbe's number were excellent. Even in Example 4 containing 75% by mass of zirconium oxide with respect to the total amount of 100 parts by mass of the components (A) and (B), the thickness is 50 μm or more and the transmittance is 80% or more. That is, it was found that the resin composition having a high content of the component (D) could provide the same transmittance as that of the resin composition not containing the component (D).

On the other hand, in Comparative Example 1 in which the component (A), the polymerizable compound having an alicyclic structure, and the component (C) are contained, the refractive index is significantly reduced as compared to Reference Example 1, and the high refractive index It was found that it is effective to contain a polymerizable compound having an aromatic ring in combination in order to obtain.

In addition, it was found that in the experimental example in which an acrylic polymer not having a fluorene skeleton is contained instead of the component (A) in Reference Example 1, the refractive index is significantly reduced as compared with Example 1.

Claims (5)

Component (A): a compound having a fluorene skeleton,
Component (B): a polymerizable compound having an aromatic ring other than the component (A) ,
Component (C): Photopolymerization initiator , and
Component (D): an inorganic compound,
Contain,
The compound having a fluorene skeleton includes a compound having a fluorene skeleton and having a (meth) acryloyloxy group,
The polymerizable compound includes a compound having two or more aromatic rings and having a (meth) acryloyloxy group,
The component (D) has a functional group capable of reacting with a (meth) acryloyl group,
The content of the component (A) is 50 to 80 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B),
The content of the component (B) is 20 to 50 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B),
The content of the component (D) is 100 to 400 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B).
Resin composition. The resin composition according to claim 1 , wherein the component (D) contains zirconium oxide. The resin composition of Claim 1 or 2 whose average particle diameter of the said (D) component is 50 nm or less. The resin composition according to any one of claims 1 to 3 , wherein the component (D) is surface-treated. The optical member provided with the component formed using the resin composition as described in any one of Claims 1-4 .