CN101592759B - Resin composition for optical material, resin film for optical material, and optical waveguide using the same - Google Patents

Abstract

The present invention provides a resin film for forming a waveguide which has high transparency and high heat resistance, while enabling formation of a thick film with high precision, this resin composition is particularly useful for a resin film which is used for forming optical waveguides. Also specifically disclosed are a resin film for an optical material using such a resin composition and an optical waveguide using such a resin film. The flexible waveguide provided by the present invention is composed of a resin film for forming a core layer and a resin film for forming two coating layers, which is characterized in that at least one of resin film for forming the two coating layers is made of a resin for forming the coating layer and a base material film, the base material film is configured at outer side of the coating layer relative to the core layer, the resin film for forming the coating layer is used for making the resin for forming the coating layer on a base material film implementing excessive bonding process.

Description

Resin composition for optical material, resin for optical material film and use its photoconduction

The application is to be on October 7th, 2005 applying date of original application, and application number is 200580034020.X, and denomination of invention is divided an application for the Chinese patent application of " resin composition for optical material, resin for optical material film and use its photoconduction ".

Technical field

The present invention relates to the good resin composition for optical material of a kind of thermotolerance, the transparency and throughput rate, resin for optical material film and use its photoconduction, and good flexible light guide and the manufacture method thereof of bendability, toughness and throughput rate.

Background technology

Along with popularizing of the Internet and LAN (LAN (Local Area Network)), for the increase corresponding to information capacity, not only in the communications field of so-called main line or access system, and between the platform in router or server unit or in the transmission of the short-range signal in platform also just in the light interconnection technique of application light signal.Concrete, use up in order to make between the platform in router or server unit or in the transmission of the short-range signal in platform, developing the optical/electrical mixed mounting substrate that is compounded with optical transmission line on electric distributing board.

The degree of freedom of the suitable use distribution of optical transmission line as this moment is higher than optical fiber, and photoconduction that can densification, wherein, has more appropriately used the photoconduction of the polymeric material of processability and economical.The polymkeric substance photoconduction is because have as mentioned above the structure that coexists with electric distributing board, so require the polymkeric substance photoconduction to have simultaneously high transparent (low conduction loss) and high-fire resistance, as such light-guide material, fluorinated polyimide (for example referring to patent documentation 1 and non-patent literature 1), deuterate silicones (for example referring to non-patent literature 2) and epoxy resin (for example referring to patent documentation 2 and non-patent literature 3) have been proposed.

, in the photoconduction of such use, in order to ensure with photoluminescence element (Guang Shou development light sub-prime) close ト レ ラ Application ス in conjunction with tolerance (Knot), the big or small General Requirements of core is 50 μ m square left and right.The thickness that this means sandwich layer must have about 50 μ m, but when for example using the waveguide material of deuterate silicones or fluorinated polyimide, although resin itself has the high-fire resistance of 300 ℃ of left and right, but waveguide material is generally low viscous solvent, therefore realize on optical/electrical mixed mounting substrate that the thickness about 50 μ m is difficult, enables namely perhaps to realize that the thickness precision is also very poor.

And, when using the waveguide material of fluorinated polyimide, resin itself has the heat-resisting quantity of 300 ℃ of left and right, and is to have the high transparent of 0.3dB/cm under 850nm at wavelength, but must heating tens of minutes～a few hours more than 300 ℃, be difficult to masking on electric distributing board during because of film forming.And because fluorinated polyimide does not have photonasty, so be not suitable for manufacture method by the photoconduction of sensitization, development, throughput rate, large tracts of landization are poor.And then, the coating liquid material comes the method for masking to make photoconduction on substrate because use, so film thickness monitoring is complicated, and because be liquid before curing at the resin that is coated with on substrate, resin trickles on substrate, is liquid problem so exist the homogeneity be difficult to guarantee thickness etc. to stem from material shape.

And the top coating after imbedding for sandwich layer will carry the photoluminescence element after considering, requirement has flatness, but when the top coating uses liquid waveguide material, protrusion pattern concavo-convex of core easily occur following, be difficult to realize planarization.

For epoxy resin, also the same with above-mentioned deuterate silicones or fluorinated polyimide light-guide material, there is the liquid problem that comes from.

That is, up to now, form the epoxy resin of use as photoconduction, use under room temperature is liquid epoxy resin always, perhaps solid epoxy is diluted the material that forms in solvent.Although their transparencys are good, have a thermotolerance of 200～280 ℃ of left and right, but owing to coming the method for masking to make photoconduction with the liquid material of coating on substrate such as spin-coating method, so its film thickness monitoring is complicated, and because the epoxy resin that is coated on substrate is liquid before curing, liquid flows on substrate, is liquid problem so exist the homogeneity that is difficult to guarantee thickness etc. to stem from material shape.

And then, there is report to claim that epoxy resin can be by adding Photoepolymerizationinitiater initiater, form the core pattern through sensitization, development method, and the high transparent with 0.1dB/cm, but the thermotolerance of epoxy resin is generally 200～280 ℃, go for above-mentioned optical/electrical mixed mounting substrate, but in order to obtain high reliability, also require higher thermotolerance.

As mentioned above, form with in resin at present photoconduction, can not have (1) high transparent concurrently, (2) high-fire resistance, (3) can form thick film accurately, and (4) throughput rate is good.

And, transmit for the high-speed and high-density signal between electronic component or between wiring substrate, in the transmission by electric distribution in the past, the mutual interference of signal or decay just become obstacle, begin to find that there is the limit in high-speed and high-density.Make the so-called light interconnection technique of using up between connecting electronic component or between wiring substrate in order to abolish this rule, to study.As light path, from considering with easy, the maneuverable viewpoint of the combination of element or substrate, the flexible light guide that possesses flexibility is fit to.

As flexible light guide, for example there are the macromolecule membrane photoconduction of record in patent documentation 3.Macromolecule membrane is spin coating Polymer Solution etc. on the substrates such as silicon, forms the bottom clad by curing.After forming sandwich layer by same method, with the formation mask patterns such as photoresist that contain Si, after forming the core pattern by dry corrosion, form the top clad by the method same with forming the bottom clad.By from the strippable substrate photoconduction, make the photoconduction of filming at last.To show especially in order easily peeling off, to use the silicon substrate of thermal oxide as substrate, after photoconduction forms, the method for flooding to peel off with hydrofluorite.

But, in the said film photoconduction by spin coating, cure and form bottom clad, sandwich layer, top each layer of clad.The formation spended time of each layer in the method, simultaneously because be coating liquid material masking on substrate, so when using the method to make photoconduction, film thickness monitoring is complicated, and at the resin that is coated with on substrate because be liquid before curing, so resin flows on substrate, exist to be difficult to guarantee that it is liquid problem that film thickness uniformity etc. stems from material shape.And, because substrate uses silicon, be not suitable for making in a large number the photoconduction of the above size of 10cm.

And then in above-mentioned manufacture method, the technique with high vacuum is dry corrosion technique, in order to make the thick multimode photoconduction of sandwich layer, must carry out dry corrosion very for a long time.

Patent documentation 1: specially permit No. 3085666 communique

Patent documentation 2: Unexamined Patent 6-228274 communique

Patent documentation 3: Unexamined Patent 7-239422 communique

Non-patent literature 1: electronics is installed association's will (ェ レ Network ト ロ ニ ク ス real dress Hui Chi), Vol.7, No.3, pp.213-218,2004

Non-patent literature 2:IEEE Journal of Lightwave Technology Vol.16, pp.1049-1055,1998

Non-patent literature 3: optics, 31 No. 2, volumes, pp.81-83,2002

Summary of the invention

The present invention in view of the above problems, its purpose be to provide a kind of for high transparent, high-fire resistance, can form high-precision thick film, and the photoconduction that throughput rate is high forms with the useful especially resin composition for optical material of resin film, uses the resin for optical material film of this resin combination and use its photoconduction, and provide a kind of and have high bendability or toughness, and good flexible light guide and the manufacture method thereof of throughput rate.

The inventor studies assiduously, and research repeatedly found that and uses specific optical polymerism compound, and uses the resin combination that contains optical polymerism compound and polymerization initiator in base polymer, can address the above problem.

That is, the present invention is

(1) a kind of resin composition for optical material, it contains (A) base polymer, (B) optical polymerism compound and (C) Photoepolymerizationinitiater initiater.

(2) a kind of resin composition for optical material, it contains as fluorenes two (methyl) acrylate of following general formula (I) expression of (B) optical polymerism compound and (C) Photoepolymerizationinitiater initiater.

(X is the group of following formula (II) expression, and Y is hydrogen or methyl, and m and n are respectively 1～20 integer.)

(R1～R16 is respectively the alkyl of hydrogen, carbon number 1～12, the alkoxy of carbon number 1～6, the alkoxy carbonyl of total carbon atom number 2～7, the aryl of carbon number 6～10 or the aralkyl of carbon number 7～9 independently.)

(3) as the resin composition for optical material of record in above-mentioned (1), wherein (B) optical polymerism compound has the ethene unsaturated group in molecule.

(4) as the resin composition for optical material of record in above-mentioned (3), wherein (B) optical polymerism compound is (methyl) acrylic acid epoxy ester (ェ Port キ シ (メ タ) ァ Network リ レ one ト) or (methyl) acrylic acid acrylic ester (ァ Network リ Le (メ タ) ァ Network リ レ one ト).

(5) as the resin composition for optical material of record in above-mentioned (3), wherein contain fluorenes two (methyl) acrylate of following general formula (I) expression in (B) composition.

(X is the group of following formula (II) expression, and Y is hydrogen or methyl, and m and n are respectively 1～20 integer.)

(R1～R16 is respectively the alkyl of hydrogen, carbon number 1～12, the alkoxy of carbon number 1～6, the alkoxy carbonyl of carbon number 2～7, the aryl of carbon number 6～10 or the aralkyl of carbon number 7～9 independently.)

(6) as the resin composition for optical material of record in above-mentioned (3), wherein contain (methyl) acrylate of following general formula (III) expression in above-mentioned (B) composition.

(R ¹⁷Be-CH ₂CH (OH) CH ₂-,-(C ₂H ₄O) _hC ₂H ₄-,-(C ₃H ₆O) _iC ₃H ₆-or-(C ₂H ₄O) _j-(C ₃H ₆O) _kC ₃H ₆-, U is-C (CH ₃) ₂-,-CH ₂-,-SO ₂-or-O-, V is hydrogen or halogen, W be hydrogen or-CH ₃Here h, i, j and k are respectively 0～10 integers.)

(7) as the resin composition for optical material of record in above-mentioned (1), wherein contain as (B) composition the compound that has 2 above epoxy radicals in molecule.

(8) resin composition for optical material as putting down in writing in any one of above-mentioned (1) or (3)～(7), wherein the number-average molecular weight of (A) base polymer is more than 5000.

(9) resin composition for optical material as putting down in writing in any one of above-mentioned (1) or (3)～(8), wherein (A) base polymer has the aromatic series skeleton on main chain.

(10) as the resin composition for optical material of record in above-mentioned (9), wherein (A) base polymer contains at least a structural unit as copolymer composition that is selected from least a of (a-1) bisphenol-A, bisphenol type epoxy compound or their derivant and is selected from (a-2) Bisphenol F, Bisphenol F type epoxy compound or their derivant.

(11) as the resin composition for optical material of record in above-mentioned (9), wherein (A) base polymer is phenoxy resin.

(12) resin composition for optical material as putting down in writing in any one of above-mentioned (1) or (3)～(8), wherein (A) base polymer is at room temperature to be the epoxy resin of solid.

(13) resin composition for optical material as putting down in writing in any one of above-mentioned (1) or (3)～(12), wherein with respect to (A) composition and (B) total amount of composition, (A) content of composition is 5～80 quality %, (B) content of composition is 20～95 quality %, and with respect to (A) composition and (B) total amount 100 mass parts of composition, (C) content of composition is 0.1～10 mass parts.

(14) resin composition for optical material as putting down in writing in above-mentioned (13), wherein with respect to (A) composition and (B) total amount of composition, (A) content of composition is 10～80 quality %, and (B) content of composition is 20～90 quality %.

(15) as any one the described resin composition for optical material in above-mentioned (1)～(14), wherein with respect to (B) composition and (C) total amount of composition, (B) content of composition is 90.0～99.9 quality %, and (C) content of composition is 0.1～10.0 quality %

(16) the resin for optical material film that is made by the resin combination of any one record in above-mentioned (1) or above-mentioned (3)～(15).

(17) as the resin for optical material film of above-mentioned (16) record, wherein above-mentioned resin for optical material film is that resin film is used in photoconduction formation, and the light conduction loss of the solidfied material of this film is below 0.5dB/cm.

(18) a kind of photoconduction, the bottom of photoconduction coating, core and top coating one of at least in used above-mentioned (17) in resin for optical material film of record.

(19) a kind of manufacture method of photoconduction, it is included in laminated optical material resin film on substrate, form the first step of bottom clad, the resin for optical material film that lamination is higher than the refractive index of this bottom clad, form the second step of sandwich layer, to this sandwich layer exposure imaging, form the third step of the core pattern of photoconduction, the resin for optical material film lower than sandwich layer refractive index with lamination, form the 4th step of top clad, at first step, the resin for optical material film that uses in second step and the 4th step be one of at least the resin for optical material film of record in above-mentioned (16) or (17).

(20) a kind of flexible light guide, it uses 1 sandwich layer to form with resin film and 2 clads formation and makes with resin film, it is characterized in that clad form with resin film be one of at least to be formed with resin and base film by clad to consist of, this base film is configured in the outside of clad with respect to sandwich layer.

(21) as the flexible light guide of record in above-mentioned (20), it is characterized in that it is masking clad formation resin on the base film of having implemented bonding processing that above-mentioned clad forms with resin film.

(22) as the flexible light guide of record in above-mentioned (20) or (21), wherein sandwich layer form form with resin film and 2 clads with resin film one of at least in resin for optical material film of putting down in writing in using above-mentioned (17).

(23) a kind of manufacture method of flexible light guide, comprise solidifying and forms by clad clad that the clad that consists of with resin and base film forms the use resin film and form and use resin, form the first step of clad, the lamination sandwich layer forms and uses resin film on this clad, the second step of lamination sandwich layer, to this sandwich layer exposure imaging, form the third step of the core pattern of photoconduction, form with lamination clad on this core pattern and use resin film, solidify clad and form the 4th step of using resin.

(24) as the manufacture method of the flexible light guide of record in above-mentioned (23), it is characterized in that it is masking clad formation resin on the base film of having implemented bonding processing that above-mentioned clad forms with resin film.

(25) as the manufacture method of the photoconduction of record in above-mentioned (23) or (24), its center core layer form with resin film and 2 clads form with resin film one of at least in use the resin for optical material film of record in above-mentioned (17).

Resin for optical material constituent of the present invention has the high transparency and high-fire resistance, and the resin for optical material film that is made by this constituent has high transparent and high-fire resistance, and can form high-precision thick film.And by using this resin for optical material film, energy throughput rate is the good photoconduction of manufacturing property well.

Description of drawings

Fig. 1 means the mode chart of the technique that forms the photoconduction pattern.

Fig. 2 is the figure of the manufacture method of explanation flexible light guide.

Symbol description

1: the bottom clad

2: substrate

3: sandwich layer

4: base material (sandwich layer forms and uses)

5: photomask

6: the core pattern

7: the top clad

8: base film (clad forms and uses)

9: the bottom clad

10: sandwich layer

11: base material (sandwich layer forms and uses)

12: photomask

13: the core pattern

14: the top clad

15: base film (clad forms and uses)

Embodiment

Resin for optical material constituent of the present invention is to contain (A) base polymer, (B) optical polymerism compound and (C) resin combination of Photoepolymerizationinitiater initiater, this resin combination contains the fluorenes with ad hoc structure two (methyl) acrylate as (B) optical polymerism compound in addition, and (C) Photoepolymerizationinitiater initiater.

(A) base polymer that here uses is to be used for guaranteeing the material of its intensity when the solidfied materials such as formation film, so long as can realize its purpose, be not particularly limited, can there are phenoxy resin, epoxy resin, (methyl) acryl resin, polycarbonate resin, polyacrylate resin, polyetheramides, polyetherimide, polyethersulfone etc. or their derivant etc.These base polymers can use separately a kind, or mix more than 2 kinds and use.

In the above-mentioned base polymer of enumerating, consider from the viewpoint that thermotolerance is high, have the aromatic series skeleton on preferred main chain, particularly preferably phenoxy resin.And, improving stable on heating aspect from carrying out three-dimensional cross-linked and consider, preferred epoxy is at room temperature particularly the epoxy resin of solid.

And when using resin combination of the present invention to carry out filming, the transparency of guaranteeing this film is important, and therefore the intermiscibility with (B) described later optical polymerism compound must be high.Preferred above-mentioned phenoxy resin and (methyl) acryl resin thus.In addition, (methyl) acryl resin here refers to acryl resin and methacrylic resin.

Above-mentioned phenoxy resin is unbodied polymkeric substance, is generally represented by following general formula (IV).

Here, n is the integer more than 1, and m is 0 or 1, and-Ro-is following general formula (V), (VI) or (VII) group of expression, or-O-.

Here, R ₁～R ₁₀H or CH ₃, CF ₃Organic group Deng expression.

In above-mentioned phenoxy resin, has the straight chain shape high molecular polymer of bisphenol A type epoxy resin of repetitive of following formula (VIII) expression because have high-fire resistance, so be preferred.

The phenoxy resin of above-mentioned straight chain shape high molecular polymer is generally by making bisphenol-A and chloropropylene oxide carry out the single stage method of polycondensation reaction, the material that the two step method that perhaps makes low-molecular-weight epoxy resin and bisphenol-A carry out addition polymerization is made, object lesson can there are Dongdu and change into the material put down in writing in " YP-50 " (trade name) that company makes, Unexamined Patent 4-120124 communique, Unexamined Patent 4-122714 communique, Unexamined Patent 4-339852 communique etc.

and, except the phenoxy resin of above-mentioned general formula (IV) expression, the polymer substance that makes in addition various 2 officials' energy epoxy resin and bisphenols carry out addition polymerization and get, bromize phenoxy resin (JP 63-191826 communique for example, JP 8-26119 communique), bisphenol-A/Bisphenol F copoly type phenoxy resin (is speciallyyed permit No. 2917884 communique, specially permit communique No. 2799401), phosphorous phenoxy resin (JP 2001-310939 communique), introduce high-fire resistance phenoxy resin (the Unexamined Patent 11-269264 communique of fluorene skeleton, Unexamined Patent 11-302373 communique) the known phenoxy resin such as.

The following phenoxy resin that represents above-mentioned bisphenol-A/Bisphenol F copoly type phenoxy resin is suitable as (A) of the present invention composition.That is, be the material that contains at least a structural unit as copolymer composition that (a-1) be selected from least a of bisphenol-A, bisphenol type epoxy compound or their derivant and (a-2) be selected from Bisphenol F, Bisphenol F type epoxy compound or their derivant.

Like this by contain take (a-1) composition and (a-2) the resin for optical material film that makes as the resin combination of the resin of copolymer composition of composition be especially suitable for use as photoconduction and form and use resin combination, by using it, pattern formative (fine rule or narrow distance between centers of tracks correspondence) in the time of more improving the interlayer adhesion of coating and core or photoconduction core pattern and form can form the little fine pattern of live width or distance between centers of tracks.

As bisphenol-A or bisphenol type epoxy compound or their derivant, what be fit to enumerate has tetrabromobisphenol A or a tetrabromobisphenol A type epoxy compound etc.And as Bisphenol F or Bisphenol F type epoxy compound or their derivant, what be fit to enumerate has tetrabromobisphenol F or a tetrabromobisphenol F type epoxy compound etc.

As (A) of the present invention base polymer, as mentioned above, what be particularly suitable for enumerating has bisphenol-A/Bisphenol F copoly type phenoxy resin, and for example Dongdu changes into the trade name " Off ェ ノ ト-ト YP-70 " that company makes.

Then, as the epoxy resin that under room temperature is solid, " ェ ピ コ-ト 1010, ェ ピ コ-ト 1009, ェ ピ コ-ト 1008 bisphenol A type epoxy resins such as (being trade name) made such as " ェ Port ト-ト YD-7020, ェ Port ト-ト YD-7019, ェ Port ト-ト YD-7017 " (being trade name) that have Dongdu to change into company to make, japan epoxy resin company.

Molecular weight about (A) base polymer, because between the platform in router or server unit or the light signal in platform transmit the film that can form 50 μ m left and right thick films with requirements such as photoconductions, preferred number average molecular weight is more than 5000, and then be preferably more than 10000, be particularly preferably more than 30000.The upper limit of molecular weight is not particularly limited, but from considering with the intermiscibility of (B) optical polymerism compound or the viewpoint of exposure imaging, is preferably below 1000000, more preferably below 500000, is particularly preferably below 200000.In addition, the number-average molecular weight in the present invention is the value after converting with gel permeation chromatography (GPC) mensuration and polystyrene standard.

(A) combined amount of base polymer with respect to (A) composition and (B) total amount of composition be preferably 5～80 quality %.Its combined amount is that 5 quality % are above, easily will contain the resin combination filming of optical polymerism compound and Photoepolymerizationinitiater initiater.Particularly more than 10 quality %, when forming film, can also easily make thickness is the above thick film of 50 μ m, so be preferred.

On the other hand, (A) composition below 80 quality %, when forming photoconduction, improves the formative of pattern, and can carry out fully photocuring reaction.Consider from above viewpoint, (A) combined amount of base polymer 20～70 quality % more preferably.

Then, (B) of the present invention optical polymerism compound is so long as can the material of polymerization is not particularly limited by the irradiation of the light such as ultraviolet ray, from the reactivity of light being considered have the compound of ethene unsaturated group in preferred molecule.Concrete, can there are (methyl) acrylate, vinylidene halide, vinyl ether, vinylpyridine, vinylphenol etc., wherein consider preferred (methyl) acrylate from the transparency and thermotolerance.

As (methyl) acrylate, can use any of 1 functionality, 2 functionalities, 3 functionalities.

In addition, (methyl) acrylate here refers to acrylate and methacrylate.

(methyl) acrylate as 1 functionality can there are methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group polyglycol (methyl) acrylate, lauryl (methyl) acrylate, iso stearyl (methyl) acrylate, 2-(methyl) acryloxy ethyl succinic acid, to cumenyl phenoxy group ethylene glycol (methyl) acrylate, 2-THP trtrahydropyranyl (methyl) acrylate, (methyl) isobornyl acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) benzyl acrylate etc.

and, can there are the 2-methyl isophthalic acid as 2 functionalities (methyl) acrylate, ammediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, the 2-methyl isophthalic acid, 8-ethohexadiol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-nonanediol two (methyl) acrylate, ethoxylation polypropylene glycol two (methyl) acrylate, the propoxylation ethoxylated bisphenol a diacrylate, ethylene glycol bisthioglycolate (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, ethoxylation bisphenol-A two (methyl) acrylate, tristane two (methyl) acrylate, ethoxylation cyclohexanedimethanol two (methyl) acrylate, 2-hydroxyl-1-acryloxy-3-methacryloxy propane, 2-hydroxyl-1,3-dimethyl allene acyloxy propane, two [4-(the 2-acryloyl-oxy base oxethyl) phenyl] fluorenes of 9,9-, two (3-phenyl-4-acryloyl group polyoxy ethoxy) fluorenes of 9,9-, bisphenol A-type, the phenol phenolic varnish type, cresols phenolic varnish type and glycidol ether type epoxy (methyl) acrylate etc.

and, as 3 above (methyl) acrylate of officials' energy, ethoxylation cyamelide three (methyl) acrylate is arranged, ethoxylated glycerol three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, ethoxylation pentaerythrite four (methyl) acrylate, pentaerythritol propoxylate four (methyl) acrylate, two trimethylolpropane four (methyl) acrylate, caprolactone modification two trimethylolpropane four (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.They can use separately or be used in combination more than 2 kinds.

(B) the optical polymerism compound can use separately a kind of compound, the compound that perhaps mixes more than 2 kinds uses, but when stating in the use (methyl) acrylate more than 2 officials' energy, can win base polymer over by any means in the 3 dimension reticulate textures that produce by polymerization and solidify, therefore preferably using at least a as (B) composition is that 2 officials can above polymerizable compound.

In the example of above-mentioned (B) composition, (methyl) acrylic acid epoxy ester is to take into account especially the transparency and stable on heating suitable compound, is the preferred material that uses in the present invention.The bisphenol A epoxy acrylate that following formula (IX) expression is arranged as (methyl) acrylic acid epoxy ester of representative.Bisphenol A epoxy acrylate can be realized high transparent because good with the phenoxy resin intermiscibility, so (A) composition uses phenoxy resin, (B) composition use bisphenol A epoxy acrylate is very preferred scheme.

In addition, this bisphenol A epoxy acrylate can be purchased EA-1020 (Xin Zhong village chemical industrial company makes, trade name).

And, consider from transparent viewpoint, also be fit to use (methyl) acrylic acid acrylic ester as (B) composition, when particularly being used in combination (methyl) acrylic resin as (A) composition, its effect is good especially.Being not particularly limited as (methyl) acrylic acid acrylic ester, is generally the goods of (methyl) acrylate of addition 1 functionality in the polymkeric substance of glycidyl acrylate.Can there are various compounds as this 1 functionality (methyl) acrylate, be for example (methyl) acrylic acid or the same with the compound of enumerating as above-mentioned 1 functionality (methyl) acrylate.

The resin for optical material film that is made by resin composition for optical material of the present invention forms the use resin film when forming photoconduction as photoconduction, need high core film and the low coating film of refractive index of refractive index that describe in detail later, but when resin for optical material film of the present invention is used as the core film, (B) composition optical polymerism compound except to have high transparent, high-fire resistance and and (A) the intermiscibility of composition, also to consider high index of refraction, therefore preferably contain fluorenes two (methyl) acrylate as constituent.Particularly preferably contain fluorenes two (methyl) acrylate of following general formula (I) expression as constituent.

Here, X is the group of following formula (II) expression, and Y is hydrogen or methyl.And m and n are respectively 1～20 integer, are preferably 1～10 integer.

Here, R1～R16 represents respectively the alkyl of hydrogen, carbon number 1～12, the alkoxy of carbon number 1～6, the alkoxy carbonyl of carbon number 2～7, the aryl of carbon number 6～10 or the aralkyl of carbon number 7～9 independently.R9～R16 respectively can be in any one position of phenyl ring, do not have these substituent parts (in formula (II) " ^*" mark) be combined with the oxygen in the skeleton of formula (I).In addition, general formula (I) and (II) in, Y is hydrogen, R1～R16 is hydrogen, m is that 1, n is that 1 material can be purchased (Xin Zhong village chemical company makes, trade name " A-BPEF ").

And, as the film of core material, consider from same viewpoint, also can use (methyl) acrylate of following general formula (III) expression.

Here, R ¹⁷Be-CH ₂CH (OH) CH ₂-,-(C ₂H ₄O) _hC ₂H ₄-,-(C ₃H ₆O) _iC ₃H ₆-or-(C ₂H ₄O) _j-(C ₃H ₆O) _kC ₃H ₆-, U is-C (CH ₃) ₂-,-CH ₂-,-SO ₂-or-O-, V is hydrogen or halogen, W be hydrogen or-CH ₃And h, i, j and k are respectively 0～10 integer.Wherein, R particularly preferably ¹⁷For-CH ₂CH (OH) CH ₂-, U is-C (CH ₃) ₂-, V is that hydrogen and W are the bisphenol-a epoxy acrylates of hydrogen, this compound can be purchased (Xin Zhong village chemical company makes, trade name " EA-1020 ").

In addition, as (B) composition, can also be also with having at least the compound of (methyl) acryloyl group in above-mentioned fluorenes two (methyl) acrylate and molecule.

As (B) of the present invention optical polymerism compound, contain the compound that has 2 above epoxy radicals in molecule and also be fit to.Concrete can there are 2 officials' energy aromatic glycidyl ethers such as bisphenol A type epoxy resin, tetrabromobisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A D type epoxy resin, naphthalene type epoxy resin; The multifunctional aromatic glycidyl ethers such as phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, bicyclopentadiene-phenol type epoxy resin, four phenylol ethane type epoxy resin; 2 officials' energy aliphatic glycidyl ethers such as polyethylene glycol type epoxy resin, polypropylene glycol type epoxy resin, neopentyl glycol type epoxy resin, hexanediol type epoxy resin; 2 officials' energy ester ring type glycidol ethers such as hydrogenation bisphenol A type epoxy resin; The multifunctional aliphatic glycidyl ethers such as trimethylolpropane type epoxy resin, D-sorbite type epoxy resin, glycerol type epoxy resin; 2 officials' energy aromatic series ethylene oxidic esters such as phthalic acid 2-glycidyl ester; 2 officials' energy ester ring type ethylene oxidic esters such as tetrahydrochysene phthalic acid 2-glycidyl ester, hexahydrobenzene dioctyl phthalate 2-glycidyl ester; N, N-2-glycidyl aniline, N, 2 officials' energy aromatic series glycidyl amines such as N-diglycidyl 5-trifluoromethylaniline; N, N, N ', N '-four glycidyl group-4,4-diaminodiphenyl-methane, 1, two (N, the N-glycidyl-amino methyl) cyclohexanes of 3-, N, N, the multifunctional aromatic series glycidyl amines such as O-triglycidyl group-para-aminophenol; 2 officials' energy alicyclic epoxy resins such as alicyclic ring diepoxy acetal, alicyclic ring diepoxy adipate, alicyclic ring diepoxy carboxylate, vinyl cyclohexene dioxide; 2 officials' energy hetero ring type epoxy resin such as diglycidyl hydantoins; The multifunctional hetero ring type epoxy resin such as triglycidyl group isocyanuric acid ester; 2 officials such as organopolysiloxane type epoxy resin can or the multifunctional epoxy silicone etc. that contains.

These common its molecular weight of compound that have 2 above epoxy radicals in molecule are 100～2000 left and right, and more preferably 150～1000 left and right, be liquid material under suitable use room temperature.And these compounds can use separately or be used in combination more than 2 kinds, and then can also use with other optical polymerism compound combinations.In addition, the molecular weight of optical polymerism compound of the present invention is measured by GPC or mass analysis.

The combined amount of above-mentioned (B) optical polymerism compound with respect to (A) composition and (B) total amount of composition be preferably 20～95 quality %.Its combined amount can easily be won base polymer over by any means and solidify more than 20 quality %, has advantages of the pattern of raising formative when forming photoconduction.On the other hand, below 95 quality %, easily by adding (A) filming that becomes to assign to, further from the angle consideration of the thick film of easy formation, more preferably below 90 quality %.From above viewpoint, (B) combined amount of optical polymerism compound 30～80 quality % more preferably.

(C) of the present invention Photoepolymerizationinitiater initiater is not particularly limited, for example the initiating agent as fluorenes two (methyl) acrylate or (methyl) acrylate can there are benzophenone, N, N '-tetramethyl-4, 4 '-diaminobenzophenone (michaelis ketone), N, N '-tetraethyl-4, 4 '-diaminobenzophenone, 4-methoxyl-4 '-dimethylamino benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 2, 2-dimethoxy-1, 2-diphenylethane-1-ketone, the 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 1, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl] 2-morpholino propane-aromatic ketones such as 1-ketone, 2-EAQ, phenanthrenequione, 2-tert-butyl group anthraquinone, prestox anthraquinone, 1,2-benzo anthraquinone, 2,3-benzo anthraquinone, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinones, 9,10-phenanthrenequione, 2-MNQ, 2, the quinones such as 3-dimethyl anthraquinone, the benzoin ether compounds such as benzoin methylether, benzoin ethyl ether, benzoin phenylate, the benzoin compounds such as benzoin, methylbenzene acyloin, ethylbenzene acyloin, the benzyl derivatives such as benzyl dimethyl ketal, 2-(adjacent chlorophenyl)-4,5-diphenyl-imidazole dimer, 2-(adjacent chlorophenyl)-4,5-two (methoxyphenyl) imidazoles dimer, 2-(adjacent difluorophenyl)-4,5-diphenyl-imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dimer etc. 2,4,5-triarylimidazoles dimer, two (2,4, the 6-trimethylbenzoyl) phenylphosphine oxide, two (2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide, 2,4, phosphine oxide class, the 9-phenylacridines, 1 such as 6-trimethylbenzoyl diphenyl phosphine oxide, the acridine derivatives such as two (9, the 9 '-acridinyl) heptane of 7-, N-phenylglycine, N-phenylglycine derivant, coumarin series compounds etc.And in 2,4,5-triarylimidazoles dimer, 22,4, the substituting group of the aryl of 5-triarylimidazoles can be identical and symmetrical compound is provided, also can be different and asymmetric compound is provided.And, as the combination of diethyl thioxanthone and dimethylaminobenzoic acid, also can make up thioxanthones based compound and tertiary amine compound.They can use separately or be used in combination more than 2 kinds.

And, consider optimization aromatic ketone and phosphine oxide class in above-claimed cpd from the transparency that improves sandwich layer and clad.

Initiating agent as epoxy resin is not particularly limited, such as there are aryl diazonium salts such as methoxybenzene diazonium hexafluorophosphoric acid esters; The diaryl group iodized salts such as Er phenyl-iodide Liu Fu phosphonium salt, diphenyl iodine hexafluoro antimonate; Triphenylsulfonium six fluorine phosphonium salts, triphenylsulfonium hexafluoro antimonate, diphenyl-4-sulfo-Phenoxyphenyl sulfonium hexafluoro antimonate, diphenyl-4-sulfo-Phenoxyphenyl sulfonium hexafluoro antimonate, diphenyl-triarylsulfonium salts such as 4-sulfo-Phenoxyphenyl sulfonium five fluorine hydroxyl stibates; The triaryl selenium salt such as triphenyl selenium Liu Fu phosphonium salt, triphenyl selenium borofluoride, triphenyl selenium hexafluoro antimonate; The dialkyl benzene formyl Methylsulfonium Salts such as dimethyl phenacyl sulfonium hexafluoro antimonate, diethyl phenacyl sulfonium hexafluoro antimonate; Dialkyl group-4-hydroxy phenyl the sulfonium salts such as 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-hydroxy phenyl benzyl methyl sulfonium hexafluoro antimonate; Alpha-hydroxy methylbenzene acyloin sulphonic acid ester, N-hydroxyl acid imide sulphonic acid ester, α-sulfonyloxy ketone, β-sulphonic acid esters such as sulfonyloxy ketone etc.These polymerization initiators can use separately or be used in combination more than 2 kinds.

The combined amount of above-mentioned (C) Photoepolymerizationinitiater initiater with respect to (A) composition and (B) total amount 100 mass parts of composition be preferably 0.1～10 mass parts.This combined amount is more than 0.1 mass parts, and lightsensitivity is abundant, and below 10 mass parts, during exposure, the absorption on the top layer of photosensitive polymer combination can not increase on the other hand, and interior lights is solidified fully.And then, when using as photoconduction, can transmission loss be increased, therefore be fit to.Consider from above viewpoint, (C) more preferably 0.2～5 quality % of the combined amount of Photoepolymerizationinitiater initiater.

And (C) content of Photoepolymerizationinitiater initiater with respect to (B) composition and (C) gross mass of composition, is preferably 0.1～10 quality % scope.On the other hand, (B) content of composition is preferably 90～99.9 quality % scopes.(C) words of the content of composition more than 0.1 quality %, photo sensitivity is abundant, words below 10 quality % on the other hand, only the surface selectivity at photoconduction solidifies, do not have and solidify inadequate problem, and can transmission loss be increased, therefore be fit to.Consider from above viewpoint, (C) more preferably 0.2～5 quality % of the content of Photoepolymerizationinitiater initiater.

And, in addition also can be as required, in resin composition for optical material of the present invention, add the so-called adjuvants such as internal mold release, antioxidant, anti-yellowing agent, ultraviolet light absorber, visible light absorber, colorant, plastifier, stabilizing agent, filling agent with the ratio of not damaging effect of the present invention.

Resin for optical material film of the present invention is made by above-mentioned resin combination, and when this film was used as photoconduction, the optical transmission loss of its solidfied material was preferably below 0.5dB/cm.Here optical transmission loss is that (SAIRON THCHNOLOGY company makes, the value of SPA-4000) measuring with prism coupled type optical characteristics determinator.

Resin for optical material film of the present invention can be dissolved in solvent by the resin combination that will contain (A)～(C) composition, be applied on base material, then desolventizing easily prepares.Solvent used herein is so long as can dissolve the material of this resin combination, just be not particularly limited, for example can use acetone, MEK, methyl cellosolve, ethyl cellosolve, toluene, N, dinethylformamide, DMA, propylene glycol monomethyl ether equal solvent or their mixed solvent.Solid component concentration in resin solution is preferably about 30～60 quality % usually.

The thickness of resin for optical material film of the present invention is not particularly limited, but dried thickness is generally 10 μ m～100 μ m.More than 10 μ m, the advantage that increases in conjunction with tolerance with photoluminescence element or optical fiber is arranged, below 100 μ m, be improved the advantage with the joint efficiency of photoluminescence element or optical fiber.According to above-mentioned viewpoint, the thickness of this film is more preferably in 30 μ m～70 μ m scopes.

And,, be not particularly limited as long as can closed optical path or imbed core about the thickness of the coating film of photoconduction, be generally 20～200 μ m.

The below describes the suitable example when the photoconduction of suitable purposes forms with resin film with resin for optical material film of the present invention in detail.

The base material that uses in the manufacture process of photoconduction formation of the present invention with resin film is to support photoconduction to form the support with film, its material is not particularly limited, but from easily peeling off photoconduction formation film described later, and the aspect with thermotolerance and solvent resistance is considered, is fit to there are the polyester such as polyethylene terephthalate; The polyolefin such as polypropylene, tygon etc.The thickness of this base material is preferably in 5～50 μ m scopes.More than 5 μ m, the advantage of easy acquisition support intensity is arranged, below 50 μ m, when pattern forms and the gap of mask little, have advantages of to form meticulousr pattern.Consider from above viewpoint, the thickness of this base material is the scope of 10～40 μ m more preferably, and then is preferably the scope of 15～30 μ m, particularly preferably 20～30 μ m.

And, for the transmitance that improves the exposure light line with reduce the coarse of core pattern sidewalls, preferably use the flexible parent metal of high transparent type.The haze value of high transparent type base material is preferably below 5%, more preferably below 3%, particularly preferably below 2%.In addition, haze value is based on JIS K7105 and measures, such as using the commercially available mensuration such as nephelometer such as NDH-1001DP (Japanese electric look industrial group make).As such base material, can obtain trade name " コ ス モ シ ャ ィ Application A1517 " or " コ ス モ シ ャ ィ Application A4100 " that Japan's textile company is made.

The photoconduction that arranges on the base material that obtains like this forms and for example can easily preserve by being wound into web-like with film.And, also can on photoconduction forms with film, protective film be set as required.In addition, above-mentioned base material and protective film are used film in order easily to peel off photoconduction formation described later, also can implement antistatic treatment etc.

Photoconduction of the present invention forms with resin film can as bottom coating, core and the top coating of photoconduction, preferably use this film at least one in them.

The below describes the manufacture method of using this resin film to form photoconduction in detail.As the method, for example can there are when having protective film after removing protective film, coat the method etc. that film makes its lamination from the bottom that base material is peeled off in substrate top heating edge crimping.Here, consider preferably under reduced pressure lamination from adhesiveness and tracing ability.The heating-up temperature of this resin film is preferably 50～130 ℃, and crimping pressure is preferably 0.1～1.0MPa left and right (1～10kgf/cm ²The left and right), its condition is not particularly limited.Then, solidify the bottom by light or heating and coat film, coat the high core film of film refractive index with same method lamination than the bottom.Minus or the eurymeric mask pattern of the resin film of lamination by being called as former figure, shine into pattern-like with active ray like this.Light source as active ray can effectively radiate ultraviolet known light source such as there are carbon arc lamp, mercury vapor arc lamp, extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, xenon lamp etc.And, also can use other photograph effectively to radiate the product of visible light with light diffuser, sunlamp etc.

Then, after exposure, remove unexposed portion by wet development, dried development etc., develop, make the core pattern.During wet the development, with an organic solvent, alkaline aqueous solution, water system developer solution etc. are corresponding to the developer solution of the composition of above-mentioned resin film, by such as spraying, shake the known methods such as dipping, brushing, beating and develop.

The safety and stable such as, alkaline aqueous solution preferred with an organic solvent as developer solution, the material that operability is good.Be that developer solution for example can there are 1,1,1-trichloroethanes, 1-METHYLPYRROLIDONE, DMF, DMA, cyclohexanone, methyl isobutyl ketone, gamma-butyrolacton etc. as above-mentioned organic solvent.These organic solvents catch fire in order to prevent, can add water in the scope of 1～20 quality %.

As the alkali of above-mentioned alkaline aqueous solution, such as alkali metal pyrophosphates such as the alkali metal phosphates such as carbonic acid alkaline metal, potassium phosphate, sodium phosphate, sodium pyrophosphate, potassium pyrophosphate such as the carbonate of alkali hydroxide metal, lithium, sodium, potassium or the ammoniums such as the oxyhydroxide that can there are lithium, sodium or potassium or supercarbonate etc.And, the alkaline aqueous solution that uses in development is such as thin solution of the sodium tetraborate of the thin solution of the NaOH of the thin solution of the sal tartari of the thin solution of the sodium carbonate that preferably there are 0.1～5 quality %, 0.1～5 quality %, 0.1～5 quality %, 0.1～5 quality % etc.And the pH of the alkaline aqueous solution that uses in development is preferably in 9～11 scope, and its temperature can be regulated according to the developability of the layer of photosensitive polymer combination.And, can sneak into surfactant, defoamer in alkaline aqueous solution, for a small amount of organic solvent of promoting to develop etc.

As above-mentioned water system developer solution, can be made by water or aqueous alkali and more than one organic solvent.The alkaline matter here for example can there are borax, sodium metasilicate, Tetramethylammonium hydroxide, monoethanolamine, ethylenediamine, Diethylenetriamine, TRIS, 1,3-diamino-propanol-2, morpholine etc. except above-mentioned substance.The pH of developer solution is preferred as far as possible little in the scope that resist is fully developed, and pH is preferably 8～12, pH more preferably 9～10.As above-mentioned organic solvent, such as there are tri acetylacetonate alcohol, acetone, ethyl acetate, the alkoxyethanol with alkoxy of carbon number 1～4, ethanol, isopropyl alcohol, butanols, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether etc.They can use separately or be used in combination more than 2 kinds.The concentration of organic solvent is preferably 2～90 quality % usually, and its temperature can be adjusted according to developability.And, can also sneak on a small quantity surfactant, defoamer etc. in the water system developer solution.

And, as required also can be in conjunction with the visualization way more than 2 kinds.As visualization way such as there are spray pattern, brushing, the beatings etc. such as impregnation method, fashion of extrusion, high-pressure fog mode.

As the processing after developing, can or carry out 0.1～1000mJ/cm about 60～250 ℃ heating as required ²The core pattern is further solidified in the exposure of left and right.

Then, the top that the lamination that uses the same method is lower than core film refractive index coats film, makes photoconduction.

Then, flexible light guide of the present invention is described.Flexible light guide of the present invention is to use 1 sandwich layer of high index of refraction to form 2 flexible light guides that clads formation is made of resin film using resin film and low-refraction, it is characterized in that clad forms with resin film at least 1 and formed with resin and base film by clad and consist of, this base film is to be configured in the outside of clad with respect to sandwich layer.Thus, can obtain to have given the flexible light guide of flexibility or the toughness of base film.And, use the photoconduction formation of film-form to use material, can solve the distinctive throughput rate of liquid material or the problem relevant to large tracts of land.And then the structure of the arranged outside base film by being formed in clad avoids clad to be exposed to the external world, makes it avoid polluting or the impact such as damage, so can improve the easy operability of photoconduction.

The base film that configures on the outside of clad can be arranged on the one side of flexible light guide at least, also can be arranged on the few flexible light guide of warpage that symmetrical structure is made on the two sides.

The base film that clad used herein forms with resin film is the support of giving photoconduction flexibility and toughness, its material is not particularly limited, but consider from the viewpoint of flexibility, toughness, be fit to there are the polyester such as polyethylene terephthalate, polybutylene terephthalate, Polyethylene Naphthalate, tygon, polypropylene, polyamide, polycarbonate, polyhenylene ether, polyether sulfides, polyarylate, liquid crystal polymer, polysulfones, polyethersulfone, polyetheretherketone, polyetherimide, polyamidoimide, polyimide etc.The thickness of base film is can be according to the flexibility of expectation and appropriate change, but is preferably 5 μ m～250 μ m.Words more than 5 μ m have the advantage of easy acquisition toughness, and the words below 250 μ m can obtain sufficient flexibility.

And, on base film, also electric distribution can be set, this moment can use preset electric distribution as base film.Perhaps, after flexible light guide is made, form electric distribution on base film.

Form as above-mentioned clad and use resin film, preferably the masking clad forms and uses resin on the base film of having implemented bonding processing.Thus, can improve the bonding force of clad and base film, suppress the unfavorable condition of peeling off of clad and base film.The bonding processing here refers to by base plate processing such as easy adhering resin coating, corona treatment, sandblasts etc., improve base film and the clad resin that forms thereon between the processing of bonding force.

Clad used herein forms with resin so long as lower than the refractive index of sandwich layer, can be not particularly limited by the resin combination of light or heat curing, can use compositions of thermosetting resin or photosensitive polymer combination.

More suitably, clad form with resin preferably by contain (A) base polymer, (B) optical polymerism compound and (C) resin combination of Photoepolymerizationinitiater initiater consist of.Wherein, about (A) composition, (B) composition and (C) composition be as mentioned above.

Clad forms can be dissolved in solvent by the resin combination that will contain (A)～(C) composition with resin film, be applied on above-mentioned base film, then desolventizing easily prepares.The above-mentioned solvent that uses in the manufacturing of solvent used herein and resin for optical material film is the same.In addition, the solid component concentration in resin solution is preferably about 30～80 quality %.

About the thickness of clad, preferred dried thickness is in 5 μ m～500 μ m scopes.More than 5 μ m, can guarantee the coating thickness that closed optical path is required, below 500 μ m, easily control equably thickness.Consider from above viewpoint, the thickness of this clad is more preferably in 10 μ m～100 μ m scopes.

And, the thickness of clad, at the initial bottom clad that forms and can be identical or different in order to the top clad of imbedding the core pattern, but in order to imbed the core pattern, the Thickness Ratio core layer thickness of preferred top clad is thick.

The sandwich layer that uses in the present invention forms that to be configured to sandwich layer with resin film higher than the refractive index of clad, can use and can form the resin combination of core pattern by active ray, and photosensitive polymer combination is fit to.Concrete, preferred use and above-mentioned clad form with the identical resin combination that uses in resin.That is, contain above-mentioned (A), (B) and (C) composition, contain as required the resin combination of above-mentioned any composition.

Sandwich layer forms can be dissolved in solvent by the resin combination that will contain (A)～(C) composition with resin film, be applied on base material, then desolventizing easily prepares.The above-mentioned solvent that uses in the manufacturing of solvent used herein and resin for optical material film is the same.Solid component concentration in resin solution is preferably about 30～80 quality % usually.

The thickness that sandwich layer forms with resin film is not particularly limited, and usually can be adjusted to dried core layer thickness in 10 μ m～100 μ m scopes.The words of core layer thickness more than 10 μ m, have advantages of that photoconduction forms enlarging in conjunction with the level tolerance of rear and photoluminescence element or optical fiber, below 100 μ m, the advantage that the joint efficiency that has photoconduction to form rear and photoluminescence element or optical fiber can improve.Consider from above viewpoint, the thickness of this film is more preferably in 30 μ m～70 μ m scopes.

It is to support photoconduction to form the support with film that sandwich layer forms the base material that uses in manufacture process with resin film, and its material is not particularly limited, can be with the manufacture process of photoconduction formation with resin film in the same material of base material that uses.

The below describes the manufacture method of flexible light guide of the present invention in detail.

At first, as first step, solidify and to form by clad clad that the clad that makes with resin and base film forms the use resin film and form and use resin, the formation clad.Form in the first step of this clad, when clad formation opposes that with the base film of resin film side arranges protective film, peel off this protective film, use up or heat to solidify clad formation resin film, form clad.

Then, as second step, the lamination sandwich layer forms and uses resin film, this sandwich layer of lamination on clad.In this second step, by add the formation of thermo-compressed sandwich layer resin film, the sandwich layer that lamination is higher than clad refractive index on above-mentioned clad.Here, consider preferably under reduced pressure lamination from adhesiveness and tracing ability.The heating-up temperature here is preferably 50～130 ℃, and crimping pressure is preferably 0.1～1.0MPa left and right (1～10kgf/cm ²The left and right) left and right, its condition is not particularly limited.Sandwich layer forms to need only with resin film and is made of sandwich layer and base material, and easily operation is preferred, and sandwich layer also can consist of separately in addition.

Then, as third step, exposure imaging sandwich layer, the core pattern of formation photoconduction.Concrete, by the minus mask pattern, with visual shape irradiation active ray.As the light source of active ray, can effectively radiate ultraviolet known light source such as there are carbon arc lamp, mercury vapor arc lamp, extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, xenon lamp etc.And, also can use other photograph effectively to radiate the product of visible light with light diffuser, sunlamp etc.

Then, when having sandwich layer to form base material with resin film, peel off this base material when residual, with wet develop to wait remove unexposed portion, develop, the formation waveguide patterns.During wet the development, using the organic solvent that is fit to the said film composition is developer solution, develops by spraying, the known method such as dipping, brushing, beating of shaking.

Organic solvent is processing after developer solution, visualization way and development and above-mentioned identical.

Then, carry out lamination and solidify clad forming the 4th step of using resin film in order to imbed the core pattern.Being formed situation about making with resin and base film by clad with resin film when clad forms during lamination, is clad to be formed be in the core patterned side with resin.The thickness of the clad of this moment is preferred as mentioned above greater than the thickness of sandwich layer.Curing is by light or heat and above-mentioned the same carrying out.

According to above-mentioned manufacture method, can greatly shorten the Production Time of the large multimode photoconduction of prior art SMIS size.

By (B) composition and (C) resin composition for optical material of the present invention that makes of composition dissolve (B) and (C) composition acquisition in solvent.As long as dissolving this resin combination, solvent used herein just is not particularly limited, for example can use 1-METHYLPYRROLIDONE, N, dinethylformamide, DMA, cyclohexanone, MEK, methyl isobutyl ketone, gamma-butyrolacton, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, acetone, toluene etc. or their mixed solvent.Resinous principle concentration in resin solution is preferably 30～80 quality % usually.

By (B) composition and (C) resin composition for optical material of the present invention that makes of composition be preferred at least one party in bottom coating, core and the top coating of photoconduction.

The following describes use by (B) composition and (C) resin composition for optical material of the present invention that makes of composition make the method for photoconduction.As the method, such as being to be coated with this resin combination by methods such as spin-coating method, infusion process, spray-on process, curtain coating method, silk screen print method, rolling methods on substrate, after the dry desolventizings such as heating or drying under reduced pressure, come cured resin by irradiation active ray or heating.This resin bed namely consists of clad.

Then, by same coating process, coating is than the high resin combination of photoconductive layer refractive index that formerly forms, with it as sandwich layer.Then, by the mask pattern of minus or eurymeric, shine active ray, remove unexposed portion with wet development, dried development etc. after exposing, develop, make the core pattern.Here, as required, can be by heating or carry out 0.1～1000mJ/cm at about 60～250 ℃ ²The photoconduction pattern is further solidified in the exposure of left and right.

Then, the coating that uses the same method, the resin that masking is lower than sandwich layer refractive index are made photoconduction.

Embodiment

Describe the present invention in detail below by embodiment, but the invention is not restricted to these examples.

Embodiment 1

(Hitachi changes into industrial group and makes to wait mass ratio to mix the acrylic acid epoxy oligomer ester, trade name " ヒ タ ロ ィ De 7851 ") and phenoxy resin (Dongdu changes into company and makes, trade name " YP-50 ") (using as solvent is the MEK of 50 mass parts with respect to 100 mass parts all resins amounts), (Tokyo changes into industrial group and makes to add the light trigger of 2 mass parts with respect to 98 mass parts all resins amounts therein, by 2, two (the 2-chlorphenyls)-4 of 2-, 4 ', 5, 5 '-tetraphenyl-1, 2 '-bisglyoxaline, 4 of same company manufacturing, 4 '-3 yuan of optical free radicals that 2-mercaptobenzimidazole that two (diethylamino) benzophenone and same company make makes produce agent), prepare photoconduction formation resin combination.(ョ シ ミ ッ essence machine company makes to use applicator, " YBA-4 ") (Japan's textile company is made at the PET film, " A4100 ") upper this resin combination of coating, at under 80 ℃ dry 10 minutes, then under 100 ℃ dry 10 minutes, solvent flashing obtains photoconduction formation resin film.This moment film thickness can be by regulating applicator gap (gap) at 5 μ m to regulating arbitrarily between 100 μ m, be 12 μ m in the present embodiment.

(name mechanism is done manufacturing to use the vacuum pressure type laminating machine, MVLP-500) under the condition of pressure 0.4MPa, temperature 60 C, form at this photoconduction of silicon wafer (thickness is 1mm) superimposed layer with heat oxide film (thickness is 1 μ m) and use resin film.With the ultraviolet ray of metal halide lamp (ァ ィ グ ラ Off ィ ッ Network ス company make, " ァ ィ De Le Off ィ Application 3000 ") with 1J/cm ²Irradiate, light-cured resin, after peeling the PET film off, then baking after carrying out under 160 ℃ of lower conditions of 1 hour, obtain sheet (ス ラ Block) photoconduction (core thickness 12 μ m).Use prism-coupled tester (Model2020) that Metricon company makes to measure the refractive index (the mensuration wavelength is 830nm) of the sheet photoconduction (core) of this moment, its as a result its as a result refractive index be all 1.583 at TE polarisation, TM polarisation.Be up under 265 ℃ of Da Wendu (15～20 seconds retention times more than 260 ℃), nitrogen atmosphere condition, its 3 times are being flowed in stove (Furukawa Electric Industrial Co., Ltd make, " サ ラ マ Application ダ ") by scolding tin is counter.

(SAIRON TECHNOLOGY company makes with prism coupled type optical characteristics determinator, SPA-4000) measure conduction loss (mensuration wavelength: the 830nm of anti-stream front and back, use the coupling oil of nD=1.60), result is that the conduction loss before and after anti-stream is respectively 0.2dB/cm, 0.3dB/cm.Can find out that photoconduction formation of the present invention has high-fire resistance with resin film, and low loss.In addition, in the present embodiment, heat oxide film is the effect of playing the bottom coating, and air plays the effect of top coating.

And, change the gap of applicator, the preparation thickness that uses the same method is the photoconduction formation resin film of 50 μ m, after using the mask pattern exposure, with DMA development (under room temperature, vibration was shaken 40 seconds), carry out pattern and form, its results verification can be made the photoconduction of live width 50 μ m.

Embodiment 2

Except replacing phenoxy resin, use solid epoxy (Dongdu changes into company and makes, trade name " ェ Port ト-ト YD-7020 ") in addition, the same with embodiment 1, obtain photoconduction formation resin film.Film thickness is 12 μ m.

The same with embodiment 1 record uses this photoconduction to form with resin film acquisition sheet photoconduction (core thickness is 12 μ m).The refractive index of measuring the sheet photoconduction (core) of this moment the same as embodiment 1, its as a result refractive index be all 1.565 at TE polarisation, TM polarisation.Be up under 265 ℃ of Da Wendu (15～20 seconds retention times more than 260 ℃), nitrogen atmosphere condition, its 3 times are being flowed in stove (Furukawa Electric Industrial Co., Ltd make, " サ ラ マ Application ダ ") by scolding tin is counter.

(SAIRON TECHNOLOGY company makes with prism coupled type optical characteristics determinator, SPA-4000) measure conduction loss (mensuration wavelength: the 830nm of anti-stream front and back, use the coupling oil of nD=1.60), result is that the conduction loss before and after anti-stream is respectively 0.2dB/cm, 0.3dB/cm.Can find out that photoconduction formation of the present invention has high-fire resistance with resin film, and low loss.

And, the gap of change applicator, the preparation thickness that uses the same method is the photoconduction formation resin film of 50 μ m, after using the mask pattern exposure, develop (under room temperature with DMA, vibration was shaken 40 seconds), to carry out pattern and form, confirmation can be made the photoconduction of live width 50 μ m.

Embodiment 3

(Hitachi changes into industrial group and makes to use the acrylic acrylate oligomer, trade name " ヒ タ ロ ィ De 7975 ") replace the acrylic acid epoxy oligomer ester, (Imperial Chemical Industries industry company makes to use acryl resin, trade name " HTR-860P-3DR " replaces phenoxy resin, in addition the same with embodiment 1, obtain photoconduction formation resin film.Film thickness is 12 μ m.

The same with embodiment 1 record uses this photoconduction to form with resin film acquisition sheet photoconduction (core thickness is 12 μ m).The refractive index of measuring the sheet photoconduction (core) of this moment the same as embodiment 1, its as a result refractive index be all 1.506 at TE polarisation, TM polarisation.Be up under 265 ℃ of Da Wendu (15～20 seconds retention times more than 260 ℃), nitrogen atmosphere condition, its 3 times are being flowed in stove (Furukawa Electric Industrial Co., Ltd make, " サ ラ マ Application ダ ") by scolding tin is counter.

(SAIRON TECHNOLOGY company makes with prism coupled type optical characteristics determinator, SPA-4000) measure conduction loss (mensuration wavelength: the 830nm of anti-stream front and back, use the coupling oil of nD=1.56), result is that the conduction loss before and after anti-stream is respectively 0.2dB/cm, 0.3dB/cm.Can find out that photoconduction formation of the present invention has high-fire resistance with resin film, and low loss.

And, the gap of change applicator, the preparation thickness that uses the same method is the photoconduction formation resin film of 50 μ m, after using the mask pattern exposure, develop (under room temperature with DMA, vibration was shaken 40 seconds), to carry out pattern and form, confirmation can be made the photoconduction of live width 50 μ m.

Embodiment 4

Ratio with 70.4 quality %, 29.6 quality % is blended in epoxy resin (the Asahi Electro-Chemical Co. Ltd's manufacturing that has 2 above epoxy radicals in molecule respectively, trade name " KRM-2110 ") and phenoxy resin (Dongdu changes into company and makes, trade name " YP-50 ", 35% solution of MEK), and, with respect to these resinous principles of 100 mass parts, (Asahi Electro-Chemical Co. Ltd makes to mix 2 mass parts Photoepolymerizationinitiater initiaters, trade name " SP-170 " is prepared photoconduction formation resin combination.(ョ シ ミ ッ essence machine company makes to use applicator, " YBA-4 ") (Japan's textile company is made at mylar, " A4100 ") upper this resin combination of coating, 80 ℃ of lower 10 minutes, solvent flashing under 100 ℃ of lower conditions of 10 minutes then, obtain photoconduction and form and use resin film.This moment film thickness can be by regulating applicator gap (gap) at 5 μ m to regulating arbitrarily between 100 μ m, be 12 μ m in the present embodiment.

(name mechanism is done manufacturing to use the vacuum pressure type laminating machine, MVLP-500) under the condition of pressure 0.4MPa, temperature 60 C, form at this photoconduction of silicon wafer (thickness is 1mm) superimposed layer with heat oxide film (thickness is 1 μ m) and use resin film, use " EXM-7172-B-00 " of ォ-Network making manufacturing with 1J/cm ²Irradiation ultraviolet radiation, light-cured resin, then baking after carrying out under 160 ℃ of lower conditions of 1 hour obtain sheet photoconduction (core thickness 12 μ m).The refractive index of measuring the sheet photoconduction (core) of this moment the same as embodiment 1, its as a result refractive index be all 1.537 at TE polarisation, TM polarisation.Be up under 265 ℃ of Da Wendu (15～20 seconds retention times more than 260 ℃), nitrogen atmosphere condition, its 3 times are being flowed in stove (Furukawa Electric Industrial Co., Ltd make, " サ ラ マ Application ダ ") by scolding tin is counter.

(SAIRON TECHNOLOGY company makes with prism coupled type optical characteristics determinator, SPA-4000) measure conduction loss (mensuration wavelength: the 830nm of anti-stream front and back, use the coupling oil of nD=1.56), result is that the light conduction loss before and after anti-stream is all 0.1dB/cm.Can find out that photoconduction formation of the present invention has high-fire resistance with resin film, and low loss.In addition, in this example, heat oxide film has been the effect that covers the bottom, air overlay upper part of the cover effect.

And, the gap of change applicator, the preparation thickness that uses the same method is the photoconduction formation resin film of 50 μ m, after using the mask pattern exposure, develop (under room temperature with DMA, vibration was shaken 40 seconds), to carry out pattern and form, confirmation can be made the photoconduction of live width 50 μ m.The results are shown in table 1.

Embodiment 5

The epoxy resin that has 2 above epoxy radicals in molecule in embodiment 4 is replaced to the commodity " KRM-2199 " by name that Asahi Electro-Chemical Co. Ltd makes, and obtain photoconduction the same as embodiment 1 forms and uses resin film in addition, carries out same evaluation.In addition, the refractive index of measuring sheet photoconduction (core) the same as embodiment 1, its as a result refractive index be all 1.529 at TE polarisation, TM polarisation.

(SAIRON TECHNOLOGY company makes with prism coupled type optical characteristics determinator, SPA-4000) measure conduction loss (mensuration wavelength: the 830nm of anti-stream front and back, use the coupling oil of nD=1.56), result is that the light conduction loss before and after anti-stream is respectively 0.1dB/cm, 0.3dB/cm.Can find out that photoconduction formation of the present invention has high-fire resistance with resin film, and low loss.

And, the photoconduction of confirming can make live width 50 μ ms the same as embodiment 4.The results are shown in table 1.

Embodiment 6

The epoxy resin that has 2 above epoxy radicals in molecule in embodiment 4 is replaced to the commodity " KRM-2408 " by name that Asahi Electro-Chemical Co. Ltd makes, and obtain photoconduction the same as embodiment 4 forms and uses resin film in addition, carries out same evaluation.In addition, the refractive index of measuring sheet photoconduction (core) the same as embodiment 1, its as a result refractive index be all 1.532 at TE polarisation, TM polarisation.

(SAIRON TECHNOLOGY company makes with prism coupled type optical characteristics determinator, SPA-4000) measure conduction loss (mensuration wavelength: the 830nm of anti-stream front and back, use the coupling oil of nD=1.56), result is that the light conduction loss before and after anti-stream is respectively 0.1dB/cm, 0.2dB/cm.Can find out that photoconduction formation of the present invention has high-fire resistance with resin film, and low loss.

And, the photoconduction of confirming can make live width 50 μ ms the same as embodiment 4.The results are shown in table 1.

Embodiment 7

Base polymer in embodiment 4 is replaced to Dongdu change into commodity " YD-7020 " (being the epoxy resin of solid under room temperature) by name that company makes, obtain photoconduction the same as embodiment 4 forms and uses resin film in addition, carries out same evaluation.In addition, the refractive index of measuring sheet photoconduction (core) the same as embodiment 1, its as a result refractive index be all 1.573 at TE polarisation, TM polarisation.

(SAIRON TECHNOLOGY company makes with prism coupled type optical characteristics determinator, SPA-4000) measure conduction loss (mensuration wavelength: the 830nm of anti-stream front and back, use the coupling oil of nD=1.60), result is that the light conduction loss before and after anti-stream is respectively 0.2dB/cm, 0.3dB/cm.Can find out that photoconduction formation of the present invention has high-fire resistance with resin film, and low loss.

And, the photoconduction of confirming can make live width 50 μ ms the same as embodiment 4.The results are shown in table 1.

Comparative example 1～3

Do not use in embodiment 4～6 beyond base polymer, trial preparation photoconduction the same as embodiment 4～6 forms and uses resin film respectively.In any situation, after solvent evaporates, can not form film, be liquid.The results are shown in table 1.

[table 1]

Embodiment 8

The as shown in table 2 mixing, prepare core and coat use resin, add MEK as 40 mass parts of solvent with respect to total amount therein, prepare core with and the coating resin varnish.(ョ シ ミ ッ essence machine company makes to use applicator, " YBA-4 ") (Japan's textile company is made to be applied to the PET film, " A-4100 ") on, 80 ℃ of lower 10 minutes, dry solvent under 100 ℃ of lower conditions of 10 minutes then, obtain photoconduction and form and use resin film.Photoconduction formed with the thickness of resin film and can regulate arbitrarily between 5～100 μ m by regulating the gap of applicator this moment, and the thickness after solidifying in the present embodiment is to be adjusted to core film 50 μ m, bottom coating 30 μ m, top coating 80 μ m.In addition, the refractive index of measure the same with embodiment 1 (measuring wavelength 830nm) the present embodiment SMIS film and coating film, the refractive index of core film is 1.586, the refractive index that coats film is 1.537.

(name mechanism is done manufacturing to use the vacuum pressure type laminating machine, MVLP-500) under pressure 0.5MPa, temperature 50 C, the condition of 30 seconds pressing times, (Hitachi changes into industrial group and makes at the FR-4 substrate, commodity are called " E-679F ") the upper strata section of depressing coating film, then use ultraviolet exposure machine (ォ-Network is made " EXM-1172 " that company of institute makes) with 1000mJ/cm ²Irradiation ultraviolet radiation (wavelength 365nm) forms bottom coating (Fig. 1 (a)).Then use above-mentioned vacuum pressure type laminating machine on the coating of bottom, at the condition laminated core film (Fig. 1 (b)) of pressure 0.5MPa, temperature 50 C, 30 seconds pressing times.Then, through photomask, with above-mentioned ultraviolet exposure machine with 1000mJ/cm ²After irradiation ultraviolet radiation (wavelength 365nm) (Fig. 1 (c)), solvent uses DMA, development core pattern (Fig. 1 (d)).Use the first alcohol and water when cleaning developer solution.

Then, condition the same when forming with the bottom coating forms the top coating, at last 160 ℃ of lower heat treated, makes photoconduction (Fig. 1 (e)).

Light source uses the LED of 855nm, and (ァ De バ Application テ ス ト company makes, Q81201) and be subjected to optical sensor (ァ De バ Application テ ス ト company makes, Q82214), ( measure photoconduction length 5,3,2cm according to cutback technique, incident optical: GI-50/125 multimode optical fiber (NA=0.20), outgoing optical fiber: SI-114/125 (NA=0.22), incident light: effective core diameter 26 μ m) measure the conduction loss of the photoconduction of making like this, result is 0.3dB/cm.And then, be up under 265 ℃ of Da Wendu (15～20 seconds retention times more than 260 ℃), nitrogen atmosphere condition, the photoconduction made 3 times is flowed stove (Furukawa Electric Industrial Co., Ltd makes by scolding tin is counter, " サ ラ マ Application ダ ") in, measure anti-stream loss deterioration condition, its result does not increase loss because of anti-stream.Can know that the photoconduction that uses photoconduction of the present invention to form with the resin film manufacturing has high-fire resistance, and lose low.

And then, the result of confirmation pattern formative, can form live width/distance between centers of tracks is 30/95 μ m, the fine pattern (table 3) of 40/85 μ m, 50/75 μ m.

Table 2

	(A) base polymer	(B) optical polymerism compound	(C) polymerization initiator
				Core is used	フェノト-ト YP-70 *1(20.4 quality %)	A-BPEF *2(39.8 quality %) EA-1020 *3(39.8 quality %)	Two (the 2-chlorphenyls)-4,4 ', 5 of 2,2-, 5 '-tetraphenyl 1,2 '-bisglyoxaline *5(1 mass parts) 4,4 '-two (diethylamino) benzophenone *6(0.5 mass parts) 2-mercaptobenzimidazole *7(0.5 mass parts)
Coat and use	フェノト-ト YP-70 *1(35.7 quality %)	KRM-2110 *4(64.3 quality %)	SP-170 *8(2 mass parts)

^*1 Off ェ ノ ト-ト YP-70: phenoxy resin (Dongdu changes into company and makes), bisphenol-A/Bisphenol F copoly type phenoxy resin

^*2 A-BPEF: fluorenes diacrylate (Xin Zhong village chemical company make), two [4-(the 2-acryloyl-oxy base oxethyl) phenyl] fluorenes of 9,9-

^*3 EA-1020: bisphenol-a epoxy acrylate (Xin Zhong village chemical company make), bisphenol A-type acrylic acid epoxy ester

^*4 KRM-2110:2 officials' energy alicyclic epoxy resins (Asahi Electro-Chemical Co. Ltd's manufacturing), alicyclic ring diepoxy carboxylate

^*Two (the 2-chlorphenyls)-4,4 ', 5 of 52,2-, 5 '-tetraphenyl-1,2 '-bisglyoxaline, Tokyo changes into industrial group and makes

^*64,4 '-two (diethylamino) benzophenone, Tokyo change into industrial group and make

^*7 2-mercaptobenzimidazoles, Tokyo change into industrial group and make

^*8 SP-170, the triphenylsulfonium hexa chloro-antimonate

Embodiment 9

In embodiment 8, (C) Photoepolymerizationinitiater initiater that table 2 SMIS is used replaces to two (2,4,6-trimethylbenzene formyl) phenylphosphine oxide (1 mass parts, the different chemical company of vapour Bart), 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone (1 mass parts, ultraviolet irradiation amount during the different chemical company of vapour Bart), and with the core pattern exposure changes 400mJ/cm into ²In addition, make flexible light guide the same as embodiment 8.In addition, use prism-coupled tester (Model2010) that Metricon company makes to measure the sandwich layer refractive index of this moment, result is 1.582.

( measure photoconduction length 5,3,2cm according to the cutback technique the same with embodiment 8, incident optical: GI-50/125 multimode optical fiber (NA=0.20), outgoing optical fiber: SI-114/125 (NA=0.22), incident light: the conduction loss of the photoconduction of effective core diameter 26 μ m) measuring is 0.1dB/cm, in the time of can finding out the initiating agent that uses in the present embodiment, has the very high transparency.And, measure the loss that the anti-stream the same with embodiment 8 causes deteriorated, its result loss increases less than 0.1dB/cm, confirms that the photoconduction of making has high thermotolerance.

Reference example 1

In embodiment 8, except Off ェ ノ ト-ト YP-70 being replaced to Off ェ ノ ト-ト YP-50 (bisphenol A type epoxy resin, Dongdu change into company and make) in addition, make photoconduction the same as embodiment 8.Conduction loss is 0.3dB/cm, although do not see yet and have the loss that is caused by anti-stream to increase, but the pattern of the live width that can form in embodiment 8 30 μ m, distance between centers of tracks 95 μ m and live width 50 μ m, distance between centers of tracks 75 μ m can not form (table 3), the pattern of live width 30 μ m, distance between centers of tracks 95 μ m is because the adhesion at coating/core interface is not enough, and the problem that the generation core is peeled off, the pattern of live width 50 μ m, distance between centers of tracks 75 μ m is because the dissolubility of unexposed section is low, so produce the residual problem of development of distance between centers of tracks.

Table 3

Embodiment 10

(Xin Zhong village chemical company makes at the fluorenes diacrylate, trade name " A-BPEF ") Photoepolymerizationinitiater initiater that adds 2 quality % in (changes into industrial group's manufacturing by Tokyo, " 2, two (the 2-chlorphenyls)-4 of 2-, 4 ', 5, 5 '-tetraphenyl-1, 2 '-bisglyoxaline ", " 4 of same company manufacturing, 4 '-two (diethylamino) benzophenone " and the ternary photopolymerization radical initiator that makes of same company " 2-mercaptobenzimidazole " made), the fluorenes diacrylate and the light trigger that are 100 mass parts with respect to total amount therein add the solvent N of 30 mass parts, the N-dimethyl acetamide, prepare photoconduction formation resin combination.Then, according to spin-coating method with the upper resin bed of making of the silicon wafer (thickness 1mm) of heat oxide film (thickness 1 μ m), 80 ℃ of lower 10 minutes, then dry desolventizing under 100 ℃ of lower conditions of 10 minutes.Then, use the ultraviolet ray of high-pressure mercury-vapor lamp with 1mJ/cm ²Shine above-mentioned resin bed, light-cured resin, and then baking after carrying out under the condition of 160 ℃, 1 hour obtain sheet photoconduction (core thickness 10 μ m).The refractive index of measuring the sheet photoconduction (core) of this moment the same as embodiment 1, its as a result refractive index be all 1.613 at TE polarisation, TM polarisation.And the heat decomposition temperature of this sheet photoconduction that the TGD-7000 that makes with ULVAC company measures is about 300 ℃, can know to have high-fire resistance.

Be up under 265 ℃ of Da Wendu (15～20 seconds retention times more than 260 ℃), nitrogen atmosphere condition, this sheet photoconduction 3 times is being flowed in stove (Furukawa Electric Industrial Co., Ltd make, " サ ラ マ Application ダ ") by scolding tin is counter.(SAIRON TECHNOLOGY company makes with prism coupled type optical characteristics determinator, SPA-4000) measure conduction loss (mensuration wavelength: the 830nm of anti-stream front and back, use the coupling oil of nD=1.62), result is that the light conduction loss before and after anti-stream is respectively 0.1dB/cm, 0.1dB/cm.Can find out that photoconduction formation of the present invention has high-fire resistance with resin combination, and low loss.In addition, in the present embodiment, heat oxide film has been the effect of bottom coating, and air has been the effect of top coating.

Embodiment 11

(Xin Zhong village chemical company makes at the fluorenes diacrylate with the ratio of fluorenes diacrylate 80 quality %, phenoxy resin 20 quality %, trade name " A-BPEF ") (Dongdu changes into company and makes, trade name " Off ェ ノ ト-ト YP-50 " to add phenoxy resin as base polymer in.Total amount 100 mass parts with respect to these resinous principles, the light trigger that adds 2 mass parts (changes into industrial group's manufacturing by Tokyo, " 2; two (the 2-chlorphenyls)-4 of 2-; 4 '; 5; 5 '-tetraphenyl-1; 2 '-bisglyoxaline ", the ternary optical free radical initiating agent that " 2-mercaptobenzimidazole " that " 4; 4 '-two (diethylamino) benzophenone " that same company makes and same company make makes), add therein the MEK as solvent of 40 mass parts, prepare photoconduction formation resin combination.(ョ シ ミ ッ essence machine company makes to use applicator, " YBA-4 ") (Japan's textile company is made at the PET film, " A-4100 ") upper this resin combination of coating, 80 ℃ of lower 10 minutes, then dry desolventizing under 100 ℃ of lower conditions of 10 minutes, obtain photoconduction and form and use resin film.This moment, photoconduction formed the gap that can pass through to regulate applicator with the thickness of resin film, to regulating arbitrarily between 100 μ m, be 12 μ m at 5 μ m in the present embodiment.

(name mechanism is done manufacturing to use the vacuum pressure type laminating machine, MVLP-500) under the condition of pressure 0.4MPa, temperature 60 C, form at this photoconduction of silicon wafer (thickness is 1mm) superimposed layer with heat oxide film (thickness is 1 μ m) and use resin film." EXM-7172-B-00 " that make manufacturing with ォ-Network is with 1J/cm ²Irradiation ultraviolet radiation, light-cured resin, then baking after carrying out under 160 ℃ of lower conditions of 1 hour obtain sheet photoconduction (core thickness 12 μ m).The refractive index of measuring the sheet photoconduction (core) of this moment the same as embodiment 1, its as a result refractive index be all 1.607 at TE polarisation, TM polarisation.Be up under 265 ℃ of Da Wendu (15～20 seconds retention times more than 260 ℃), nitrogen atmosphere condition, its 3 times are being flowed in stove (Furukawa Electric Industrial Co., Ltd make, " サ ラ マ Application ダ ") by scolding tin is counter.

(SAIRON TECHNOLOGY company makes with prism coupled type optical characteristics determinator, SPA-4000) measure conduction loss (mensuration wavelength: the 830nm of anti-stream front and back, use the coupling oil of nD=1.62), result is that the conduction loss before and after anti-stream is respectively 0.2dB/cm, 0.2dB/cm.Can find out that photoconduction formation of the present invention has high-fire resistance with resin film, and low loss.

Embodiment 12

In embodiment 11, replace phenoxy resin, (Dongdu changes into company's manufacturing, and trade name " ェ Port ト-ト YD-7020 " is in addition, and is the same with embodiment 11, obtains the sheet photoconduction to use under room temperature epoxy resin as solid.The refractive index of measuring the sheet photoconduction (core) of this moment the same as embodiment 1, its as a result refractive index be all 1.604 at TE polarisation, TM polarisation.Be up under 265 ℃ of Da Wendu (15～20 seconds retention times more than 260 ℃), nitrogen atmosphere condition, this sheet photoconduction 3 times is being flowed in stove (Furukawa Electric Industrial Co., Ltd make, " サ ラ マ Application ダ ") by scolding tin is counter.(SAIRONTECHNOLOGY company makes with prism coupled type optical characteristics determinator, SPA-4000) measure conduction loss (mensuration wavelength: the 830nm of anti-stream front and back, use the coupling oil of nD=1.62), result is that the conduction loss before and after anti-stream is respectively 0.2dB/cm, 0.2dB/cm.Can find out that photoconduction formation of the present invention has high-fire resistance with resin film, and low loss.

Embodiment 13

According to the mixing ratio shown in above-mentioned table 2, prepare sandwich layer and clad resin combination, adding therein with respect to total amount is the ethyl cellosolve as solvent of 40 mass parts, prepare sandwich layer with the clad resin varnish.

(ョ シ ミ ッ essence machine company makes to use applicator, " YBA-4 ") (Japan's textile company is made to be coated on the PET film, trade name " コ ス モ シ ャ ィ Application A1517 ", it is thickness 16 μ m) upper that (clad forms and uses resin film: use the bonding treated side in volume, sandwich layer forms uses resin film: use the outer non-treated side of volume), 80 ℃ of lower 10 minutes, dry solvent under 100 ℃ of lower conditions of 10 minutes then, obtain sandwich layer and clad and form and use resin film.This moment, the thickness of film can be regulated arbitrarily between 5～100 μ m by regulating the gap of applicator, and the thickness after solidifying in the present embodiment is to be adjusted to sandwich layer 40 μ m, bottom clad 20 μ m, top clad 70 μ m.

With ultraviolet exposure machine (ォ-Network makes " EXM-1172 " of manufacturing) with 1000mJ/cm ²Irradiation ultraviolet radiation (wavelength 365nm), photocuring bottom clad formation resin film (with reference to Fig. 2 (a)).Then, (name mechanism is done manufacturing, and MVLP-500) under pressure 0.4MPa, temperature 70 C, the condition of 30 seconds pressing times, the lamination sandwich layer forms with resin film (with reference to Fig. 2 (b)) on this clad to use the vacuum pressure type laminating machine.Then, through the photomask (minus) of wide 40 μ m, with above-mentioned ultraviolet exposure machine with 1000mJ/cm ²After irradiation ultraviolet radiation (wavelength 365nm) (referring to Fig. 2 (c)), make core pattern development (referring to Fig. 2 (d)) with ethyl cellosolve and DMA with the solvent of the mass ratio mixing of 8: 2.The cleaning of developer solution is to use the first alcohol and water.Then, form at same lamination laminated top clad and use resin film, carry out the heat treated under ultraviolet ray irradiation and 110 ℃, prepare flexible light guide (referring to Fig. 2 (e)).

In addition, the refractive index of sandwich layer and clad is measured with the prism-coupled tester (Model2010) that Metricon company makes, and result is under wavelength 850nm, and sandwich layer is 1.584, and clad is 1.537.

Light source uses the LED of 855nm, and (ァ De バ Application テ ス ト company makes, Q81201), ( measure photoconduction length 5,3,2cm according to cutback technique, incident optical: GI-50/125 multimode optical fiber (NA=0.20), outgoing optical fiber: SI-114/125 (NA=0.22), incident light: effective core diameter 26 μ m) measure the conduction loss of the flexible light guide of making like this, result is 0.3dB/cm.

And, with the rod of radius 2mm, that it is curling, measure its bendability, toughness, its result does not produce photoconduction and breaks, and perhaps the problem of the interface peel of clad and base film or clad and sandwich layer, have high bendability, toughness as can be known.

Embodiment 14

In embodiment 13; (C) Photoepolymerizationinitiater initiater that core in table 4 is used is instead of two (2; 4; the 6-trimethylbenzoyl) phenylphosphine oxide (1 mass parts; the different chemical company of vapour Bart), 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone (1 mass parts; ultraviolet irradiation amount during the different chemical company of vapour Bart), and with the core pattern exposure changes 400mJ/cm into ²In addition, make photoconduction the same as embodiment 13.In addition, use prism-coupled tester (Model2010) that Metricon company makes to measure the sandwich layer refractive index of this moment, result is 1.582.

The transmission loss of measuring flexible light guide the same as embodiment 13, result are 0.1dB/cm, when using as can be known the initiating agent of the present embodiment, have the very high transparency.

Embodiment 15

With the mixing ratio shown in table 4, prepare sandwich layer and clad resin combination, adding therein with respect to total amount is the ethyl cellosolve as solvent of 40 mass parts, resin varnish in preparation sandwich layer use and clad.

Table 4

	(A) base polymer	(B) optical polymerism compound	(C) polymerization initiator
				Core	フェノト-ト YP-70 *1(20 mass parts)	A-BPEF *2(39 mass parts) EA-1020 *3(39 mass parts)	Two (2,4,6-trimethylbenzoyl) phenylphosphine oxide *9(1 mass parts) 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone *10(1 mass parts)
Coating	フェノト-ト YP-70 *1(35 mass parts)	KRM-2110 *4(62.5 mass parts)	SP-170 *8(2 mass parts) SP-100 *11(0.5 mass parts)

^*1～ ^*4 Hes ^*8 as before

^*9 pairs of (2,4,6-trimethylbenzoyl) phenylphosphine oxide: the different chemical company manufacturing of vapour Bart

^*10 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone: the different chemical company manufacturing of vapour Bart

^*11 SP-100: aromatics, Asahi Electro-Chemical Co. Ltd makes

(ョ シ ミ ッ essence machine company makes to use applicator, " YBA-4 ") (Dong Li company makes at polyamide film, trade name " ミ Network ト ロ Application " thickness 12 μ m) on corona treatment face, the coating clad forms and uses varnish, (Japan's textile company is made at the PET film, trade name " コ ス モ シ ャ ィ Application A1517 ", thickness 16 μ m) be coated with cloth wick formation varnish on non-treated side, 80 ℃ of lower 10 minutes, dry solvent under 100 ℃ of lower conditions of 10 minutes then, obtain sandwich layer and clad and form and use resin film.This moment, the thickness of film can be regulated arbitrarily between 5～100 μ m by the gap of regulating applicator, and the thickness after solidifying in the present embodiment is regulated and become sandwich layer 40 μ m, bottom clad 20 μ m, top clad 70 μ m.

With ultraviolet exposure machine (ォ-Network makes " EXM-1172 " of manufacturing) with 1000mJ/cm ²Irradiation ultraviolet radiation (wavelength 365nm), photocuring bottom clad formation resin film (with reference to Fig. 2 (a)).Then, (name mechanism is done manufacturing, and MVLP-500) under pressure 0.4MPa, temperature 70 C, the condition of 30 seconds pressing times, the lamination sandwich layer forms with resin film (with reference to Fig. 2 (b)) on this clad to use the vacuum pressure type laminating machine.Then, through the photomask (minus) of wide 40 μ m, with above-mentioned ultraviolet exposure machine with 400mJ/cm ²After irradiation ultraviolet radiation (wavelength 365nm) (referring to Fig. 2 (c)), make core pattern development (referring to Fig. 2 (d)) with ethyl cellosolve and DMA with the solvent of the mass ratio mixing of 8: 2.The cleaning of developer solution is to use the first alcohol and water.Then, form at same lamination laminated top clad and use resin film, with " the ァ ィ De Le Off ィ Application 3000 " of ァ ィ グ ラ Off ィ ッ Network ス company manufacturing with 3000mJ/cm ²Irradiation ultraviolet radiation (wavelength 405nm) then carries out heat treated under 160 ℃, preparation flexible light guide (referring to Fig. 2 (e)).

In addition, the refractive index of sandwich layer and clad is measured with the prism-coupled tester (Model2010) that Metricon company makes, and result is under wavelength 850nm, and sandwich layer is 1.582, and clad is 1.539.

Light source uses the LED of 855nm, and (ァ De バ Application テ ス ト company makes, Q81201), ( measure photoconduction length 5,3,2cm according to cutback technique, incident optical: GI-50/125 multimode optical fiber (NA=0.20), outgoing optical fiber: SI-114/125 (NA=0.22), incident light: effective core diameter 26 μ m) measure the conduction loss of the flexible light guide of making like this, result is 0.1dB/cm, loses very little.

And be up under 265 ℃ of Da Wendu (15～20 seconds retention times more than 260 ℃), nitrogen atmosphere condition, the flexible light guide made 3 times is flowed stove (Furukawa Electric Industrial Co., Ltd makes by scolding tin is counter, " サ ラ マ Application ダ ") in, mensuration is increased by the loss that anti-stream causes, result is less than 0.1dB/cm, when base film used polyamide as can be known, flexible light guide had high thermotolerance.

And then, with the rod of radius 2mm, that it is curling, measure its bendability, toughness, its result does not produce photoconduction and breaks, and perhaps the problem of the interface peel of clad and base film or clad and sandwich layer, have high bendability, toughness as can be known.

Embodiment 16

In embodiment 13, beyond (non-treated side) upper coating clad forms with resin film the volume of PET film, prepare flexible light guide the same as embodiment 13.At this moment, with the rod result that it is curling of radius 2mm, producing some peeling off on the interface of clad and base film, crack on flexible light guide, is sufficient bendability and toughness but demonstrate for practicality.

Embodiment 17

To with embodiment 8 in record the same core film for preparing of method and coat film (thickness is 10 μ m), the prism-coupled tester (Model2020) that uses Metricon company to make is measured refractive index and birefringence.The results are shown in table 5.Measure wavelength, be all there is no birefringence when having high index of refraction for each, is good optical material.

And, to with embodiment 8 in record the same core film for preparing of method and coat film (thickness is 70 μ m), the spectrophotometer (model U-3410) that uses the Hitachi to make, measure the light penetration of resin for optical material film (, thickness 70 μ ms the same with the core film composition of embodiment).Any film of result all has the transmitance more than 90% in the visible region of 400～800nm, be the good resin for optical material film of the transparency.

Table 5

Embodiment 18～27

The resin combination of the various embodiments described above of table 6 record of formation thickness 10 μ m on silicon substrate, preparation resin for optical material film, the prism-coupled tester (Model2020) that use Metricon company makes is measured refractive index and birefringence (measuring wavelength 830nm).And, measure light penetration with the method the same with embodiment 17.The results are shown in table 6.

Resin for optical material film for embodiment 18～24 does not all have birefringence, is the very good optical material of the transparency.In addition, the resin for optical material film of embodiment 25～27 not only has high refractive index, and birefringence is little, and is the very good optical material of the transparency.

Table 6

Industrial applicibility

Resin composition for optical material of the present invention and the resin for optical material film transparency and the excellent heat resistance that are made by this resin combination, such as being used as photoconduction, lens, optics with encapsulant, optics bonding agent, light guide plate, diffraction grating etc., be especially suitable for use as the photoconduction resin film.In addition, can also be used for other coating materials, resist etc.When using with resin film as photoconduction, can have high transparent and high-fire resistance, and can form high-precision thick film.Thereby, by the bottom of photoconduction coating, core and top coating one of at least in use film of the present invention, photoconduction that can excellent.And, according to the present invention, can make large-area film, can throughput rate make well photoconduction.

Claims (6)

1. flexible light guide, using 1 sandwich layer to form with resin film and 2 clads formation makes with resin film, it is characterized in that two sides that 2 clads form with resin film are formed with resin and base film by clad to consist of, this base film is configured in the outside of clad with respect to sandwich layer, it is to implement masking clad formation resin on the base film of bonding processing that described clad forms with resin film, wherein, the thickness 5 μ m of described base film～250 μ m, the material of described base film is by polyester, tygon, polypropylene, polyamide, polycarbonate, polyhenylene ether, polyether sulfides, polyarylate, liquid crystal polymer, polysulfones, polyethersulfone, polyetheretherketone, polyetherimide, polyamidoimide, it is a kind of that polyimide is selected.

2. flexible light guide as claimed in claim 1, is characterized in that described bonding processing is easy adhering resin coating or corona treatment.

3. flexible light guide as claimed in claim 1 or 2, it is characterized in that described sandwich layer form form with resin film and described 2 clads with resin film one of at least in use resin for optical material film, described resin for optical material film by contain (A) base polymer, (B) optical polymerism compound and (C) resin composition for optical material of Photoepolymerizationinitiater initiater make, the light conduction loss of the solidfied material of this film is below 0.5dB/cm.

4. the manufacture method of a flexible light guide is characterized in that comprising solidifying forming by clad clad that the clad that consists of with resin and base film forms the use resin film and forming and use resin, the first step of formation clad, the lamination sandwich layer forms and uses resin film, the second step of lamination sandwich layer on this clad, this sandwich layer is carried out exposure imaging, form the third step of the core pattern of photoconduction, and lamination forms by clad the clad that consists of with resin and base film and forms and use resin film on this core pattern, this clad is formed be in this core patterned side with resin, and the curing clad forms the 4th step with resin, it is to implement masking clad formation resin on the base film of bonding processing that described clad forms with resin film, wherein, the thickness 5 μ m of described base film～250 μ m, the material of described base film is by polyester, tygon, polypropylene, polyamide, polycarbonate, polyhenylene ether, polyether sulfides, polyarylate, liquid crystal polymer, polysulfones, polyethersulfone, polyetheretherketone, polyetherimide, polyamidoimide, it is a kind of that polyimide is selected.

5. the manufacture method of flexible light guide as claimed in claim 4, is characterized in that described bonding processing is easy adhering resin coating or corona treatment.

6. as the manufacture method of claim 4 or 5 described flexible light guides, it is characterized in that described sandwich layer form form with resin film and described 2 clads with resin film one of at least in use resin for optical material film, described resin for optical material film by contain (A) base polymer, (B) optical polymerism compound and (C) resin composition for optical material of Photoepolymerizationinitiater initiater make, the light conduction loss of the solidfied material of this film is below 0.5dB/cm.

Images