JP2003128731A - Resin composition, resin composition for optical waveguide and its cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for an optical waveguide, solving a problem caused by a solvent, and excellent in processing property, and its cured material. SOLUTION: This resin composition is characterized by having (A) a urethane methacrylate compound which is a reacted product of (a) a compound expressed by the general formula (1) with (b) 2-isocyanatoethyl methacrylate, and (B) an ethylenically unsaturated group-containing compound other than the component (A).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition and a cured product thereof. More specifically, it relates to a resin composition particularly suitable for an optical waveguide and a cured product thereof.

2. Description of the Related Art Quartz is often used as a material for optical waveguides, but it has a problem that it is difficult to fabricate a large area having a high processing temperature. Recently, research on plastic waveguides using polymethylmethacrylate, etc. has progressed from the viewpoint of ease of processing. Even when such a resin is used, the resin is applied to the substrate in a state of being dissolved in a solvent. After that, in order to remove the solvent to form the core portion and the like, the solvent must be removed at an appropriate rate when removing the solvent. When the removal rate is high, bubbles or voids are generated or internal strain is generated. If the removal rate is low,
It had the drawback of taking a long time. When the removal temperature is increased, bubbles or voids may be generated and internal strain may occur due to the difference in coefficient of thermal expansion between the resin and the substrate.
Further, when a soluble resin is used for the optical waveguide, it is necessary to prevent the resin portion already formed when the clad portion and the core portion are formed from melting. Therefore, it has been necessary to introduce a cross-linking component into the resin or change the resin components in the core and clad portions. Optical transmission loss factor in optical waveguide, high frequency of infrared vibration absorption, absorption loss such as ultraviolet absorption due to electronic transition, density
Scattering loss due to Rayleigh scattering due to concentration fluctuation is mentioned, and external factors include absorption loss due to transition metal, OH group, and other impurities, impurities such as dust and bubbles, irregularity of core / cladding interface, fluctuation of core diameter, and microbending. -Scattering loss due to structural imperfections such as orientation birefringence. Regarding Rayleigh scattering, the coexistence of regions having different refractive indices is not preferable, and those exhibiting a microphase-separated structure such as crystalline polymer, block copolymer, or graft copolymer in the optical waveguide are not preferable. Further, in order to suppress fluctuations in the solid due to thermal motion, a resin that is three-dimensionally cured by ultraviolet rays or the like is desired rather than a linear polymer. Also, peeling at the core / clad interface also causes transmission loss, so the clad resin has good adhesion to the core material,
Adhesiveness is required. Therefore, it is desired that the core part and the clad part have similar components. The refractive index of the core of the optical waveguide is required to be higher than that of the cladding. It is preferable that the cladding material of a general multimode waveguide has a refractive index difference of 2 to 3% or more of that of the core material. Further, in the case of optical waveguide in a single mode, when the cross section of the core part is a square having a side of 8 μm, a clad having a refractive index as small as 0.3% is required. The refractive index fluctuation of the material is 1000
A precision of 5 minutes is required. Therefore, the refractive index range (1.45 to 1.45) of silicon resin, polymethacrylate resin, polycarbonate resin, etc., which is often used for the clad material, is used.
1.60) that can control the core material (refractive index 1.46 to 1.
62) was desired.

[0002]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a resin composition for an optical waveguide which is excellent in processability and a cured product thereof.

[0003]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific urethane methacrylate compound (A) and an ethylenically unsaturated group-containing compound (B) other than the component (A) are used.
The resin composition containing as a main component can control the refractive index to some extent by changing the composition.These resins have a low viscosity before curing and are excellent in applicability such as spin coating. When they were applied to a layer, they found that they were excellent in light transmission and were extremely excellent in flatness, and completed the present invention.

That is, the present invention provides the compound (a) represented by (1) and the general formula (1).

[0005]

[Chemical 4]

(In the formula (1), R is

[Chemical 5] , Base or

[Chemical 6] And Z represents H, a C ₁ -C ₁₃ alkyl group or a fluoro group. And a urethane methacrylate compound (A) which is a reaction product of 2-isocyanate-ethyl methacrylate (b), and an ethylenically unsaturated group-containing compound (B) other than the component (A). ,
(2), a resin composition according to (1) containing a photopolymerization initiator (C), (3), a resin composition for an optical waveguide (1)
Alternatively, the present invention relates to the resin composition according to (2) and the cured product of the resin composition according to any one of (4) and (1) to (3).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition suitable for the optical waveguide of the present invention is a specific urethane methacrylate compound (A).
And an ethylenically unsaturated group-containing compound (B) other than the component (A).

In the present invention, the urethane methacrylate compound (A) is used. The urethane methacrylate compound (A) can be obtained by reacting the compound (a) represented by the general formula (1) with 2-isocyanatoethyl methacrylate (b).

Specific examples of the compound (a) represented by the general formula (1) include:

[0010]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[0011]

[Chemical 12]

[0012]

[Chemical 13]

[0013]

[Chemical 14]

[0014]

[Chemical 15]

[0015]

[Chemical 16]

And the like.

The reaction ratio of the components (a) and (b) is
It is preferable to react 0.5 to 1.1 equivalents of the isocyanate groups in the component (b) with respect to 1 equivalent of the hydroxyl group in the component (a), and it is particularly preferable to react 0.95 to 1.05 equivalents. .

It is preferable to use a reaction catalyst to accelerate the reaction. Specific examples of the reaction catalyst include tin compounds such as dibutyltin dilaurate and di (n-butyl) tin di (2-ethylhexanoate). The amount of the reaction catalyst used is 50 ppm to 50% in the reaction mixture.
1000 ppm is preferred.

It is preferable to use a reaction solvent, and as the reaction solvent, an organic solvent inert to the isocyanate group and the hydroxyl group can be preferably used. As a specific example of the organic solvent, the reaction temperature is preferably 20 to 100 ° C, particularly preferably 30 to 80 ° C.

In the present invention, the ethylenically unsaturated group-containing compound (B) other than the component (A) is used. Specific examples of the component (B) include (meth) acrylate monomers, (meth) acrylate oligomers, maleimide compounds,
Examples thereof include vinyl ether compounds and N-vinyl compounds.

Specific examples of the (meth) acrylate monomers include dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate and tri-. Bromophenyl (meth) acrylate, methoxyphenyl (meth) acrylate, cyanophenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
Polyethylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, carbitol (meth)
Monofunctional (meth) acrylates such as acrylates. Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,4-butylene glycol di (Meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol dipolyethoxydi (meth ) Acrylate, neopentyl glycol polypropoxydi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (or tetra) (meth) acrylate neopentyl Calls of ε- caprolactone adduct di (meth) acrylate, trimethylolpropane ε-
Caprolactone adduct tri (meth) acrylate, pentaerythritol ε-caprolactone adduct tri- or tetra (meth) acrylate, dipentaerythritol penta- or hexa (meth) acrylate, dipentaerythritol ε-caprolactone adduct poly ( (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate tetrabromobisphenol A polyethoxydi (meth) acrylate, bisphenol A
Examples thereof include polyfunctional (meth) acrylates such as polyethoxydi (meth) acrylate, bisphenol hexafluoropropyl polyethoxydi (meth) acrylate and hydrogenated bisphenol hexafluoropropyl polyethoxydi (meth) acrylate.

Specific examples of (meth) acrylate oligomers include polyester (meth) acrylate, urethane (meth) acrylate and epoxy (meth) acrylate.

Specific examples of the polyester (meth) acrylate include (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5
A polyol component such as pentanediol, cyclohexane-1,4-dimethanol, bisphenol A polyethoxydiol, hydrogenated bisphenol A, trimethylolpropane and maleic acid, succinic acid, fumaric acid, adipic acid, phthalic acid, isophthalic acid, Hexahydrophthalic acid,
Polymethacrylic acid such as tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid and the like, and a (meth) acrylate of polyester polyol which is a reaction product thereof; Examples thereof include polyfunctional polyester (meth) acrylates such as (meth) acrylates of cyclic lactone-modified polyester polyols, which are reaction products of acids and their anhydrides with ε-caprolactone.

As a specific example of the urethane (meth) acrylate, a reaction product of an organic isocyanate compound, a polyol compound and a hydroxyl group-containing (meth) acrylate compound can be mentioned as a typical example.

Specific examples of the organic polyisocyanate include P-phenylene diisocyanate, m-phenylene diisocyanate, P-xylene diisocyanate and m.
-Xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate and naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate,
4,4'-dicyclohexylmethane diisocyanate,
Aliphatic or alicyclic diisocyanates such as hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; one or more burettes of isocyanate monomers, or polyisocyanates such as isocyanates obtained by trimerizing the above diisocyanate compound; and the like. To be

Specific examples of the polyol compound include the above-mentioned polyol component, polyester polyol, cyclic lactone-modified polyester polyol and the like.

Specific examples of the hydroxyl group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and cyclohexanedimethanol mono (meth). Acrylate, 4
-Hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy-
3-phenoxypropyl (meth) acrylate etc. can be mentioned.

Specific examples of the epoxy (meth) acrylate include a product obtained by reacting an epoxy resin containing a bifunctional or higher epoxy group with (meth) acrylic acid.

Specific examples of the epoxy resin include bisphenol A diglycidyl ether and hydrogenated bisphenol A.
Diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, tetrabromobisphenol A diglycidyl ether, 1,3-bis [1-
(2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl] benzene,
1,4-bis [1- (2,3-epoxypropoxy)-
1-trifluoromethyl-2,2,2-trifluoroethyl] benzene, 4,4'-bis (2,3-epoxypropoxy) octafluorobiphenyl, spiroglycol diglycidyl ether, polyethylene glycol diglycidyl ether, phenol Typical examples are novolac type epoxy resins, but the present invention is not limited thereto.

As specific examples of maleimide compounds, any compound containing a maleimide group can be used.
Examples thereof include a 1 to 3 functional maleimide compound described in JP-A-58-40374 and a maleimide group-containing urethane oligomer described in JP-A-3-12414.

Further, as typical examples, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, N-allylmaleimide, Nn-butylmaleimide, N-2. -Methyl-propylmaleimide, N-cyclohexylmaleimide, N-2-ethylhexylmaleimide, N- (2-
Dimethylaminoethyl) maleimide, N- (1-methoxymethylpropyl) maleimide, N, N'-1,6-hexane bismaleimide, bis (3-N-maleimidopropyl) polytetramethylene glycol, bis (2-N-
Maleimidopropyl) polypropylene glycol, bis (2-N-maleimidoethyl) polyethylene glycol, 1,2 (1,3 or 1,4) -bis (N-maleimidomethyl) cyclohexane,

[0032]

[Chemical 17]

[0033]

[Chemical 18]

[0034]

[Chemical 19]

And maleimide compounds in which hydrogen atoms bonded to unsaturated carbon atoms in the maleimide groups of these maleimide compounds are substituted with chlorine atoms, bromine atoms, methyl groups, ethyl groups, methoxy groups and the like. be able to.

Specific examples of vinyl ether compounds include hydroxymethyl vinyl ether, chloromethyl vinyl ether, hydroxyethyl vinyl ether, 1,
4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 4-hydroxybutyl vinyl ether, trimethylolpropane trivinyl ether, cyclohexanedimethanol mono- or divinyl ether, cyclohexane mono- or divinyl ether, triethylene glycol divinyl ether polytetramethylene Examples thereof include glycol divinyl ether, polyurethane polyvinyl ether, polyester polyvinyl ether and the like.

Specific examples of N-vinyl compounds include N
-Vinylpyrrolidone, N-vinylcaprolactam, N-
Examples thereof include vinylformamide and N-vinylacetamide.

Preferred examples of the ethylenically unsaturated group-containing compound (B) other than the component (A) include acrylate monomers, acrylate oligomers and maleimide compounds.

In the present invention, a photopolymerization initiator (C) is used as an optional component. Specific examples of the photopolymerization initiator (C) include 2,2-diethoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, benzophenone and 1- (4-isopropylphenyl) -2-hydroxy-2-methyl. Propan-1-one, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, benzoin ethyl ether, benzoin isobutyl ether,
Examples thereof include benzoin isopropyl ether, 1-hydroxycyclohexyl phenyl ketone, methylbenzisoformate, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

In the resin composition for an optical waveguide of the present invention, the ratio of the components (A) to (C) to be used is (A) component 1
The component (B) is preferably 10 to 500 parts by weight, particularly preferably 20 to 200 parts by weight, based on 00 parts by weight, and the total amount of the components (A) + (B) is 100 parts by weight.
The component (C) is preferably 0 to 10 parts by weight, particularly preferably 0.05 to 6 parts by weight.

In the present invention, if necessary, a silane coupling agent, a titanium coupling agent, a flexibility imparting agent, a characteristic modifier and the like can be added. The properties of the resin composition can be modified by adding these materials alone or in combination to the main component.

For example, as the silane coupling agent added to enhance the adhesiveness of the resin composition of the present invention, γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ
-Aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane,
N-β- (aminoethyl) -β- (aminoethyl) -γ
-Aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β- (N-vinyl Benzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloric acid group, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-
Anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, vinyltriethoxy Silane, γ-methacryloxypropyltris (2-methoxyethoxy) silane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

The resin composition of the present invention can be obtained by mixing and dissolving the components (A) to (C) and the above-mentioned coupling agent, etc., and filtering in a clean room.

As a method for producing an optical waveguide in the present invention, the clad is slightly different when an ordinary polymer resin is used and when an ultraviolet curable resin similar to the core material is used.
As an example,

(1) A resin having a refractive index smaller than that of the core to be the lower clad is applied to an arbitrary substrate. After coating, the solvent is removed by heating and drying. When an ultraviolet curable resin is used here, it suffices that the resin is applied and then cured by ultraviolet rays. By using these cured resins, the step of removing the solvent can be omitted. (2) The resin of the present invention, which serves as a core, was applied thereon, and then was irradiated with ultraviolet rays through a negative mask having a waveguide pattern to be cured. After that, when this sample was developed with an organic solvent, only the light irradiation part was cured according to the mask pattern, and a waveguide pattern could be produced. (3) Thereafter, a polymer resin for clad or an ultraviolet curable resin is applied on this, and the solvent is removed or the resin is cured by ultraviolet rays. Here, it is desirable that the lower clad and the clad on the side surface of the core and the upper clad to be finally formed have the same refractive index, and the same material is more preferable. Furthermore, when an ultraviolet curable resin is used for the clad, the uppermost surface can be flattened. In this case, a multi-layered optical wiring becomes possible, and in case of multi-layering, the above (2) and (3) may be repeated.

[0046]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. (Synthesis Example of Urethane Methacrylate Compound (A)) Synthesis Example 1 1,4-bis (hexafluoro-2-hydroxy-2-)
Propyl) cyclohexane 415.9 g, di (n-butyl) tin dilaurate 0.18 g and P-methoxyphenol 0.2 g were charged and heated to 60 ° C. with stirring, and then 2-isocyanatoethyl methacrylate 310 g was added dropwise in about 1 hour. Then, the reaction was continued for about 2 hours, and it was confirmed that no isocyanate group remained, and the reaction was terminated to obtain a liquid pale yellow substance. Refractive index of product (20 ℃
(-589 nm) was 1.435, and the components of the following structural formula were the main components.

[0047]

[Chemical 20]

Example 1 The product obtained in Synthetic Example 1 78.
3 g, 1,6-hexanediol diacrylate 2
A resin composition (a) prepared from 1.7 g and 3.0 g of 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator) was prepared. The refractive index of the resin composition (a) after curing was 1.457 at a wavelength of 589 nm.

The resin composition (a) prepared in this example was laminated on a silicon substrate by a spin coating method to a thickness of 10 μm and irradiated with ultraviolet rays to be cured. Next, 49.5 g of the product obtained in Synthesis Example 1 and 5 of phenoxyethyl acrylate
The resin composition (b) prepared from 0.5 g and / or 3.0 g of hydroxycyclohexyl phenyl ketone (photopolymerization initiator) was applied to a thickness of 5 μm by spin coating.

Next, ultraviolet rays were irradiated through a negative mask having a waveguide pattern, and then this sample was developed with γ-butyrolactone to prepare a waveguide pattern. Then, on this waveguide pattern and the lower clad layer,
The resin composition (a) was applied to a thickness of 15 μm and irradiated with ultraviolet rays to be cured to prepare an optical waveguide. By this operation, the core portion made of the cured product of the resin composition (b) having a refractive index of 1.500 after curing and the refractive index after curing of 1.
A multimode channel waveguide having a lower clad layer and an upper clad layer made of a cured product of the resin composition (a) of 457 could be produced.

The obtained optical waveguide was cut into a length of 5 cm, and the optical waveguide loss was examined by using a He-Ne laser beam having a wavelength of 633 nm. The loss was 0.3 dB / cm.

[0052]

As described above, according to the present invention, since the core material which does not use the solvent is used, the problem caused by the solvent is solved and the waveguide forming process is simplified. Further, since the flattening is easy, it is possible to realize an optical waveguide capable of multilayer optical wiring.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H047 PA02 PA15 PA24 PA28 QA05                 4J100 AE09Q AE10Q AE61Q AE64Q                       AE70Q AE76Q AL04Q AL05Q                       AL08Q AL09Q AL10Q AL62Q                       AL63Q AL66P AL66Q AM14Q                       AM45Q AM54Q AM55Q AQ06Q                       AQ08Q BA02P BA03Q BA05Q                       BA08Q BA38P BA40Q BB01Q                       BB03Q BB18P BC04P BC04Q                       BC07Q BC08Q BC09Q BC43P                       BC43Q CA04 DA63 JA32

Claims (4)

[Claims] 1. A compound (a) represented by the general formula (1): (In the formula, R is Or [Chemical 3] And Z represents H, a C ₁ -C ₁₃ alkyl group or a fluoro group. And a urethane methacrylate compound (A) which is a reaction product of 2-isocyanate-ethyl methacrylate (b), and an ethylenically unsaturated group-containing compound (B) other than the component (A). . 2. The resin composition according to claim 1, which contains a photopolymerization initiator (C). 3. The resin composition according to claim 1, which is a resin composition for an optical waveguide. 4. A cured product of the resin composition according to claim 1.