CN1863829A

CN1863829A - Light refractive index modulation polymer, light refractive index modulation polymer composition and method of controlling refractive index

Info

Publication number: CN1863829A
Application number: CN 200480028838
Authority: CN
Inventors: 川口佳秀; 诸石裕; 井上彻雄; 宗和范
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2003-10-03
Filing date: 2004-10-01
Publication date: 2006-11-15
Anticipated expiration: 2024-10-01
Also published as: CN100424102C

Abstract

A subject for the invention is to provide a method of refractive index regulation by which the refractive index of an optical polymer molding can be efficiently changed without necessitating a complicated step, such as the step of oxidizing beforehand, and which when used for producing an optical device, imparts excellent transparency thereto. Another subject is to provide a photochemically refractive-index-changing polymer or photochemically refractive-index-changing polymer composition for use in the method. The invention relates to a method of refractive index regulation characterized in that either a photochemically refractive-index-changing polymer which is a polymer of one or more monomers comprising an acrylic vinyl monomer represented by CH 2 =C (R 1 ) C (=O) O-R 2 =CH 2 (wherein R 1 is hydrogen or methyl and R 2 is a saturated or unsaturated hydrocarbon group having 1-20 carbon atoms, provided that the monomer may have one or more heteroatoms and halogen atoms in the molecule) as an essential ingredient and which has radial-polymerizable side-chain vinyl groups remaining in the molecule or a composition containing this polymer is irradiated with a radiation, e.g., ultraviolet, to react the vinyl groups and thereby cause a density change so as to result in a refractive-index increase ( n) through the irradiation of 0.005 or more.

Description

Light refractive index modulation polymer, light refractive index modulation polymer composition and specific refractory power control method

Technical field

The present invention relates to light refractive index modulation polymer or light refractive index modulation polymer composition, and the method for regulating their specific refractory poweres, described polymkeric substance or polymer composition are with radiation exposures such as for example ultraviolet rays the time, and their specific refractory power increases.

Background technology

All the time, hanker after researching and developing various optics, for example optical fiber, optical diffraction gratings, optical memory and optical integrated circuit.Recently, as the material of these optics, workability, polymer materials flexible and other character excellence just receive publicity.

When the preparation optics, arbitrarily the technology of the specific refractory power of accurate trim is absolutely necessary.Celebrated this technology is with the situation that is used for inorganic materials, for example Yi Xia method: wherein use the Ge-doped glass of rayed, and with the specific refractory power of change glass, and the preparation optical diffraction gratings.

Under the situation of polymer materials, disclosed the technology of preparation optical diffraction gratings, wherein comprise polymkeric substance and be dispersed in the polymkeric substance material of active low molecular compound when photochemical reaction with laser radiation, inducing photochromic reactions (photobleaching), and change specific refractory power (referring to patent documentation 1) thus.Also disclosed following technology, used photobleaching to generate so-called graded index material (graded-refractive-index material, GRIN material) in this technology, wherein specific refractory power changes (referring to patent documentation 2) continuously.

In these technology, use the material that obtains by mixing or low molecular compound mixed the material that obtains in the polymer molecule with low molecular compound.Situation about existing is, low molecular compound shows the enhanced light absorption ratio, and hindered device and have enough transparencies.

In addition, carried out following effort: only use rayed, and do not mix low molecular compound, improve poly-(methyl methacrylate) specific refractory power (PMMA), PMMA is with as the typical polymers of optical applications and celebrated.When passing through with the 325nm rayed, this technology causes 0.051 refractive index difference, and this is enough big to optics.But in this technology, in order to give PMMA with reactivity, the pre-oxidation methyl methacrylate monomer carries out polymerization then.Therefore, the problem of existence is that this preparation needs plenty of time and step complexity.

Reported that when there not being pre-oxidation, and during the polymerization methyl methacrylate monomer, the specific refractory power of PMMA did not increase (referring to non-patent literature 1) at all with rayed the time.Also reported, and tended to make the backbone breaking of PMMA when shining, and reduce its density (referring to non-patent literature 2) with the shorter light of wavelength (for example, 0.2537 μ m).The equational reason of Lorentz-Lorenz also proposes in the document, because can not improve specific refractory power.

(patent documentation 1)

JP-A-7-92313 (2-3 page or leaf)

(patent documentation 2)

JP-A-9-178901 (2-6 page or leaf)

(non-patent literature 1)

M.J.Bowden，E.A.Chandross，and I.P.Kaminow，Applied Optics，Vol.13，P.113(1974)

(non-patent literature 2)

W.J.Tomlison，I.P.Kaminow，E.A.Chandross，R.L.Fork and W.T.Silfvast，Applied Physics Letters，Vol.16，P.486(1970)

Summary of the invention

As mentioned above, in the correlation technique of specific refractory power control method, there is following situation: by the abundant printing opacity of the optics of these methods preparations, and since the monomeric necessity of pre-oxidation for example, the step complexity, and this causes efficient to be damaged.

In these cases, the purpose of this invention is to provide the method for regulating specific refractory power,, can change the specific refractory power of optic polymer moulded product effectively, and need not complicated step, for example preoxidized step by this method; And this method can be used for preparing optics, gives excellent transparency to optics.Another object of the present invention provides light refractive index modulation polymer or the light refractive index modulation polymer composition that is used for this method.

In order to overcome the problems referred to above, the present inventor has carried out deep research.As a result, they have found a kind of method that effectively obtains the polymkeric substance of the residual vinyl side chain (radical-polymerizable side-chain vinyl group) that free redical polymerization arranged in the molecule by the specific aggregation technology.Further find that if the film of being made by the composition of this polymkeric substance or this polymkeric substance with radiation exposures such as for example ultraviolet rays makes vinyl side chain generation crosslinking reaction, great changes will take place for density so, and can effectively change (increase) specific refractory power.In addition, even after the irradiation, also keep excellent transparency.That is to say, found to obtain to regulate the novel method of optical mode goods specific refractory power.So finished the present invention.

That is to say, the present invention relates to light refractive index modulation polymer, it is characterized in that: this polymkeric substance is to comprise following general formula, (1) Biao Shi vinylformic acid vinyl monomer, one or more monomers of (acrylic vinyl monomer) are as the polymkeric substance of neccessary composition, and this polymkeric substance is residual in molecule a free redical polymerization, (radial-polymerizable) vinyl side chain, and when using radiation exposure, this polymkeric substance increases by irradiation experience 0.005 or bigger specific refractory power, (Δ n)

CH ₂＝C(R ¹)C(＝O)O-R ²＝CH ₂ (1)

(R wherein ¹Be hydrogen atom or methyl, R ²For having the saturated or unsaturated alkyl of 1-20 carbon atom, this monomer can have one or more heteroatomss and/or one or more halogen atom in molecule).

The invention still further relates to light refractive index modulation polymer composition, it is characterized in that: described composition comprises light refractive index modulation polymer with above-mentioned structure and is selected from least a in light trigger, sensitizer and the chain-transfer agent, and when using radiation exposure, said composition increases (Δ n) (measuring with the m-Line method of TE pattern) by irradiation experience 0.005 or bigger specific refractory power.

The invention still further relates to light refractive index modulation polymer composition, it is characterized in that: described composition comprises following polymkeric substance and is selected from least a in light trigger, sensitizer and the chain-transfer agent, described polymkeric substance is to comprise the vinylformic acid vinyl monomer of following general formula (1) expression one or more polymer of monomers as neccessary composition, and this polymkeric substance is the residual vinyl side chain that free redical polymerization is arranged in molecule

CH ₂＝C(R ¹)C(＝O)O-R ²＝CH ₂ (1)

(R wherein ¹Be hydrogen atom or methyl, R ²For having the saturated or unsaturated alkyl of 1-20 carbon atom, this monomer can have one or more heteroatomss and/or one or more halogen atom in molecule), and when using radiation exposure, said composition increases (Δ n) (measuring with the m-Line method of TE pattern) by irradiation experience 0.005 or bigger specific refractory power.

The invention still further relates to the method for regulating specific refractory power, it is characterized in that: have the light refractive index modulation polymer or the light refractive index modulation polymer composition of above-mentioned structure with radiation exposure, make this polymkeric substance or said composition increase (Δ n) (measuring) thus with the m-Line method of TE pattern by irradiation experience 0.005 or bigger specific refractory power.

Particularly, the present invention can provide the method for the adjusting specific refractory power with above-mentioned structure, and wherein said ray is ultraviolet ray, and described polymkeric substance or composition with ultraviolet ray with 10J/cm ²Or littler irradiation dose is shone.

The invention still further relates to the method for preparing light refractive index modulation polymer, it is characterized in that: use contain rare earth metal as the metal complex catalyst in active centre as polymerization initiator, make one or more monomer generation anionoid polymerizations as the vinylformic acid vinyl monomer of comprising of neccessary composition of following general formula (1) expression

CH ₂＝C(R ¹)C(＝O)O-R ²＝CH ₂ (1)

Particularly, the present invention can provide the method for preparing light refractive index modulation polymer with above-mentioned structure, and the wherein said rare earth metal that contains is the metal complex of following general formula (2) expression as the metal complex in active centre:

(Cp1)(Cp2)Mr-(R) _p·(L) _q (2)

(wherein Cp1 and Cp2 independently are the cyclopentadienyl of unsubstituted cyclopentadienyl or replacement separately, and Cp1 can directly be connected mutually with Cp2 or connect by connecting base; Mr is that valency is the rare earth of r, and r is the integer of 2-4; R is hydrogen atom or the straight chained alkyl with 1-3 carbon atom; L is the solvent with coordination ability; P is the number of R, and q is the number of L, respectively the do for oneself integer of 0-2 of p and q, and select p to make itself and r satisfy relational expression r=p+2).

According to the light refractive index modulation polymer (this polymkeric substance is the residual vinyl side chain that free redical polymerization is arranged in molecule) of the invention described above or according to the light refractive index modulation polymer composition of the invention described above, can pass through with suitable irradiation dose, moulded product with these polymkeric substance of radiation exposure such as for example ultraviolet ray or composition, thereby (at will) increases the specific refractory power of described moulded product arbitrarily, and need not complicated step, for example, as the preoxidized step in the related art.

In addition, by random copolymerization or block copolymerization, copolymerization can more effectively make specific refractory power change as the various monomers of the comonomer composition of described polymkeric substance.

And in the present invention, any low molecular compound does not mix in the moulded product.Therefore, when the present invention was used to prepare optics, this device had excellent transparency.The refractive index difference that the present invention obtains is 0.005 or bigger, and this is enough big value to optics.

Description of drawings

Fig. 1 shows light refractive index modulation polymer (poly-(methyl methacrylate), feature PMMA) that obtains among the embodiment 1 ¹H-NMR figure.

Fig. 2 is Fig. 1 ¹Part among the H-NMR figure is amplified, its expression main chain methyl, and be used to calculate tacticity.

Fig. 3 is presented in the nitrogen atmosphere with uviolizing embodiment 5 (not having chain-transfer agent as promotor) poly-(methacrylic vinyl acetate) (PVMA) during poly-(methacrylic vinyl acetate) film of film and embodiment 6 and 7 (having chain-transfer agent as promotor) figure of the characteristic relation between ultraviolet integration light quantity (integrated quantity) and the refractive index difference.

Embodiment

Main points of the present invention are, with the residual polymkeric substance that the vinyl side chain of free redical polymerization is arranged in the radiation exposure molecule, make vinyl side chain generation crosslinking reaction, and based on the variable density of gained, increase the specific refractory power of optic polymer moulded product thus.

Residual in the molecule have the polymkeric substance of the vinyl side chain of free redical polymerization to be preferably poly-(methacrylic vinyl acetate) (being designated hereinafter simply as PVMA).In optic polymer, PVMA has excellent transparency, is not easy to take place double refraction, and has the physical strength of gratifying molded moral character peace weighing apparatus.In addition, during by radiation exposure, it has maximum refractive index difference.Therefore, PVMA is specially adapted to the present invention.Containing PVMA also is preferred as the multipolymer of component.

The example of ray comprises α-ray, beta-rays, gamma-radiation, neutron beam, electron beam and ultraviolet ray.Yet ultraviolet ray is special ideal.This is because use ultraviolet ray to have the following advantages, and for example can carry out the simplification of irradiator, and be not easy to occur the film deterioration.

Ultraviolet wavelength is not specifically limited,, and changes the structure of polymkeric substance thus and make density polymer that big the variation be taken place as long as wavelength makes this ultraviolet ray can make vinyl side chain generation crosslinking reaction.For example, although because ultraviolet wavelength changes along with exposure intensity etc., so can not determine ultraviolet wavelength ad lib, it is preferably 20-450nm, is in particular 250-350nm.

Consider ultraviolet wavelength to be sent, suitably select ultraviolet source.The example of ultraviolet source comprises high voltage mercury lamp, low pressure mercury lamp, metal halide lamp and ultraviolet laser.For irradiation, shine in order to use ultraviolet ray with specific wavelength, can use wavelength filter.

Too low ultraviolet irradiation intensity is inappropriate, because too low intensive irradiation can not have the polymkeric substance generation photochemical reaction of free redical polymerization group in the inducing molecule, so can not obtain the change of specific refractory power.On the contrary, when intensity is too high, the situation that exists moulded product to become opaque or become fragile.Therefore, consider these, suitably determine exposure intensity.

For example, proper irradiation intensity is about 0.001-3W/cm ²Although it changes with ultraviolet wavelength to be sent.Intensity is preferably 0.1-1W/cm ²

Consideration is determined ultraviolet irradiation time suitably with the specific refractory power that obtains.That is to say, by selecting to have the irradiation time of desired value, can regulate specific refractory power arbitrarily, this is because the specific refractory power of moulded product of the present invention increases continuously along with the carrying out of uviolizing.Irradiation time changes with ultraviolet wavelengths/intensities.Yet, for example, being the ultraviolet ray of 280-300nm, with 300mW/cm with wavelength region ²Intensity shine PVMA for example moulded product so that specific refractory power increases at 0.01 o'clock, suitable irradiation time is about 0.5-2 minute.

Advantageously ultraviolet integration light quantity is adjusted to 10J/cm ²Or littler, be in particular 5J/cm ²Greater than 10J/cm ²Irradiation may produce the film deterioration, and from the angle of time and required cost, this also is unpractiaca.

When uviolizing, just irradiated moulded product can be remained on high temperature.The reactivity that this has improved the polymkeric substance of the residual vinyl side chain that free redical polymerization arranged in the molecule can more effectively change specific refractory power thus.For example, can in the temperature range that is not higher than the moulded product melt temperature, select suitable temperature.Yet by for example, under the situation that PVMA makes, suitable temperature is about 40-70 ℃ at moulded product.

When so increasing specific refractory power by uviolizing, especially, for general purpose, the angle from the actual use of this method need not to shine in the presence of rare gas element.Yet in the presence of as rare gas elementes such as nitrogen or argon gas, shining also is ideal.In this case, easily with lower irradiance, realize the bigger variation of specific refractory power, this is the surface oxidation that has suppressed film/air interface.

When under this condition, shining with ultraviolet ray, the side chain generation crosslinking reaction of residual free redical polymerization in the polymer molecule.The result is, the density of moulded product increases, and the specific refractory power of moulded product is increased.As this crosslinking reaction, can effectively utilize any crosslinking reaction, as long as it can increase density, for example partial cross-linked moulded product.

Incidentally, by method of the present invention, can obtain to be at most 0.01 specific refractory power increase.Yet, in fact, for optics such as optical fiber and optical diffraction gratings, 0.005 or bigger refractive index difference be exactly enough big value.

In the present invention, (wavelength 633nm), is measured the specific refractory power of light refractive index modulation polymer by m-Line method (prism-coupled method) to use He-Ne laser.In this case, in TE (transverse electric) pattern (the plane glazing polarising pattern that is being parallel to mould material) and TM (transverse magnetic) pattern (polarising pattern on perpendicular to the plane of mould material), measure.Yet the specific refractory power of measuring based on the TE pattern is estimated the increase of specific refractory power in the present invention.

Particularly in optical waveguide/optical integrated circuit, the difference between TE mode refractive index and the TM mode refractive index very much not is required, because this means high light propagation loss, optical information becomes a phase gradually.Therefore, need the little material of refractive index difference between TE pattern and the TM pattern, promptly have the material of little polarization dependent loss (PDL).Therefore, the refractive index difference between TE pattern and the TM pattern is desirably 0.00100 or littler, is preferably 0.00080 or littler.

As can be known, photochemistry of the present invention changes refractive index materials and comprises vinylformic acid (ester) material from above-mentioned general formula (1).Therefore, compare with the material that is commonly used for optical waveguide, this material has lower double refraction, therefore advantageously has low PDL.

When utilizing the invention described above to regulate the method for specific refractory power, can prepare various optics.For example,, form the parts of high refractive index, can prepare optical waveguide/optical integrated circuit thus by mask uviolizing flat die goods.

In addition,, form interference fringe with uviolizing fibrous moulded product, the specific refractory power of periodic variation fiber on the length direction of fiber thus, thus can prepare optical diffraction gratings.And also can and select following condition with convergences such as lens ultraviolet ray: under this condition, the parts around the focus can experience the reaction that polarization increases, thereby have increased the specific refractory power that is positioned at the zone of specific position on the moulded product depth direction.The core (core part) that this method can be used for preparing the three-dimensional optical holder or forms optical fiber.

Light refractive index modulation polymer of the present invention is above-mentioned polymkeric substance, and described polymkeric substance is the residual vinyl side chain that free redical polymerization is arranged in molecule.That is to say that described polymkeric substance is to comprise the vinylformic acid vinyl monomer of following general formula (1) expression one or more polymer of monomers as neccessary composition, and this polymkeric substance residual vinyl side chain that free redical polymerization is arranged in molecule,

CH ₂＝C(R ¹)C(＝O)O-R ²＝CH ₂ (1)

The example of this polymkeric substance comprises: (a) homopolymer of the vinylformic acid vinyl monomer of general formula (1) expression; (b) multipolymer of the vinylformic acid vinyl monomer of two or more general formulas (1) expression; (c) the vinylformic acid vinyl monomer of one or more general formulas (1) expressions and one or more other monomeric multipolymer.These two kinds of multipolymers can be segmented copolymer or random copolymers.

The example of the vinylformic acid vinyl monomer of general formula (1) expression comprises: methacrylic vinyl acetate, methacrylic acid vinyl ethyl ester, methacrylic acid vinyl monooctyl ester, the own ester of methacrylic acid vinyl, methacrylic acid vinyl butyl ester, vinyl acrylate and vinylformic acid vinyl ethyl ester.But described monomer should not be construed as and is confined to these examples.From the suitability of general-use and the angle of availability, using the methacrylic vinyl acetate is special ideal.

But can be any copolymerisable monomer with the monomer of vinylformic acid vinyl monomer copolymerization, it is inert to the catalyzer that is used for anionoid polymerization or does not make catalyst deactivation.But the angle from copolymerized ability is preferably (methyl) acrylate, for example methyl methacrylate and Jia Jibingxisuanyizhi.What can also use is to contain those of one or more halogen atoms, for example trifluoroethyl methacrylate; Contain one or more heteroatomic those, methacrylic acid diethyllaminoethyl ester for example.Even have the monomer of the functional group that makes catalyst deactivation,, can make this monomer useful by the described functional group of end-blocking.For example, by with end-blocking hydroxyl in advance such as trimethyl silyl, can make hydroxyethyl methylacrylate etc. useful.Similarly, also can make (methyl) acrylic compound useful with carboxyl.

That is to say, the transparency, manufacturing cost equal angles from film character, moulded work, have the optimized combination of kind make the polymer materials that constitutes moulded work, and this combination specific refractory power changing than under the low irradiance, because copolymerization has improved the initial reactivity of side chain vinyl.

The vinylformic acid vinyl monomer of mutual-through type (1) expression is not specifically limited with the ratio of other monomer (for example above monomer that shows), only otherwise the change of the required specific refractory power of infringement when using radiation exposure.Usually, when other monomeric consumption is 10-70 mole % based on all monomeric amounts, particularly during 10-50 mole %, can presents the advantage of copolymerization, and not reduce the reactivity of the vinyl side chain of vinylformic acid vinyl monomer.

For obtaining light refractive index modulation polymer of the present invention, preferably use anionic polymerization initiator.Under the situation of using radical polymerization initiator, between polymerization period, not only the vinyl side chain is consumed, thereby makes the vinyl that can obtain to be used to realize refraction index changing, and polymerization generates the network polymer (gel) that is insoluble to solvent.On the other hand, be widely used as the organometallic compound of anionic polymerization initiator, for example BuLi and Grignard reagent (Grignard reagent) are not desirable, this is because the vinyl pendant moiety experiences crosslinking reaction between polymerization period, and because the productive rate and the molecular weight of the polymkeric substance that obtains are low.

Therefore, contain the catalyzer that rare earth metal is used as anionic polymer as the metal complex catalyst in active centre in the present invention's use, to obtain described polymkeric substance.

Term " thulium " is meant the 3rd family's metal herein, for example Sc, Y, lanthanon or actinide elements, and term " active centre " is meant the site with monomer coordination or keyed jointing, its direct initiated polymerization.This metal complex catalyst is also referred to as metalloscene catalyst.The example of this metalloscene catalyst comprises the complex compound of complex compound, indenyl and metal ion of cyclopentadienyl and metal ion and the complex compound of fluorenyl and metal ion.In these, particularly preferred is the complex compound of cyclopentadienyl and metal ion.

This metal complex catalyst to be used is preferably the metal complex of following general formula (2) expression:

(Cp1)(Cp2)Mr-(R) _p·(L) _q (2)

Under Cp1 in general formula (2) and the Cp2 situation for the cyclopentadienyl of replacement, substituting group is preferably methyl or trimethyl silyl.Substituent number is preferably 3-5.

The example of Cp1 or Cp2 comprises C ₅H ₅, C ₅(CH ₃) ₅, C ₅H ₂(CH ₃) ₃, C ₅(CH ₂CH ₃) ₅, C ₅H ₂(CH ₂CH ₃) ₃, C ₅H ₂[CH (CH ₃) ₂] ₃, C ₅H ₂[Si (CH ₃) ₃] ₃And C ₅H ₂[CH (CH ₃) ₂] ₃

Cp1 can directly be connected mutually with Cp2 or connect by connecting base.It is desirable to especially, Cp1 interconnects by being connected base with Cp2.

Connecting base is preferably-(CH ₂) _n[Si (CH ₃) ₂] _m-[wherein n and the m integer of 0-3 of respectively doing for oneself (m+n) is 1-3] is preferably dimetylsilyl (n is 0, and m is 1) or dimethylene (n is 2, and m is 0) especially.Connect base and can be heteroatomic groups such as for example containing ether oxygen atom.

In above-mentioned general formula (2), M is a rare earth, and it is as the active centre, and valency is r.Preferably, it is yttrium (Y), ytterbium (Yb), samarium (Sm) or lutetium (Lu).Its valency (r) is 2,3 or 4, is preferably 2 or 3 especially.

R is hydrogen atom or the straight chained alkyl with 1-3 carbon atom, is preferably methyl.L has the solvent of coordination ability.Preferably, it is preferably ether solvents for containing one or more heteroatomic solvents.Preferred ether solvents is a cyclic ether solvents, for example tetrahydrofuran (THF) and tetrahydropyrans, ether, t-butyl methyl ether etc.

The metal complex of particularly preferred above-mentioned general formula (2) expression is the metal complex that following arbitrary general formula is represented:

(Cp ^*) ₂Sm ^III-(CH ₃)·(THF) (3)

(Cp ^*) ₂Yb ^III-(CH ₃)·(THF) (4)

(Cp ^*) ₂Y ^III-(CH ₃)·(THF) (5)

(Cp wherein ^*

Be

1,2,3,4,5-pentamethyl-cyclopentadienyl, THF are tetrahydrofuran (THF)).

The rare earth metal that has that is used as polymerizing catalyst among the present invention is preferably 0.01-10 mole % as the amount of the metal complex catalyst in active centre, is preferably 0.1-5 mole % especially, based on polymerisable monomer.Under the too low situation of the amount of metal complex catalyst, be difficult to carry out anionoid polymerization.On the other hand, the amount of metal complex catalyst is too high, often causes the problem about polymer performance (for example molecular weight and molecular weight distribution).

Ideally, under the situation that does not have water and oxygen, carry out anionoid polymerization.Preferably, at inert gas atmosphere, for example carry out polymerization in nitrogen or the argon gas atmosphere.And, ideally, in the presence of solvent, carrying out polyreaction, solvent is preferably non-polar solvent, and is preferably the aromatics non-polar solvent especially, for example benzene, toluene or dimethylbenzene.

Between polymerization period, ideally the amount of polymerisable monomer is adjusted to 5-30 weight %, based on solvent.When monomeric amount was lower than 5 weight %, existence can not obtain enough high-molecular weight possibilities.When this amount surpassed 30 weight %, the possibility of existence was that the viscosity of system may increase between polymerization period, thereby causes changing into the transformation efficiency reduction of polymkeric substance.

Polymerization temperature is adjusted to is preferably 100 ℃ or lower, be preferably-95 ℃ to+30 ℃ approximately especially, most preferably be-95 ℃ to-25 ℃.The temperature that polyreaction is carried out is low more, and the three-dimensional regularity of the polymkeric substance of generation and degree of syndiotacticity (will describe after a while) often obtain more the improvement.

The polymkeric substance residual vinyl side chain that unreacted free redical polymerization is arranged in its molecule that obtains like this.The per-cent of the vinyl that these are remaining is preferably 90% or higher, and more preferably 95% or higher.

Can determine the per-cent of vinyl side chain of the free redical polymerization of remained unreacted, for example ¹H-NMR spectrum.For example, under poly-(methacrylic vinyl acetate) situation (PVNA), this per-cent can calculate from the area ratio at peak that is attributable to vinyl deutero-proton (about 4.9ppm) and the peak that is attributable to alpha-position methyl deutero-proton (1.3-0.6ppm).

It is 70% or higher polymkeric substance that the light refractive index modulation polymer of the present invention that obtains by above-mentioned anionic polymerisation process is desirably three-dimensional regularity with degree of syndiotacticity (rr) expression.When this polymkeric substance had this three-dimensional regularity, it had extremely high glass transition point (Tg) and excellent thermotolerance.

That is to say, have the light refractive index modulation polymer that obtains by polymerization under the situation that rare earth metal exists as the metallocene catalyzer in active centre, the degree of syndiotacticity (rr) of polymkeric substance that promptly has the vinyl side chain of free redical polymerization in the molecule can be 70% or higher.

The common description below of degree of syndiotacticity.

When the carbon atom of each repeating unit that constitutes the chain polymer molecular backbone has two connected not homoatomics or atomic radical (substituting group), be that stereoisomerism takes place at the center with the carbon atom.When any adjacent repeating unit along this main polymer chain always had relative configuration, this polymkeric substance was called syndyotactic polymer so.When any adjacent repeating unit along this main chain has identical configuration, this polymkeric substance is called isotactic polymer so.When the configuration along any adjacent repeating unit of this main chain is random, this polymkeric substance is called nonstereospecific polymer so.In addition, in comprising the polymer chain of all configurations, the per-cent of syndiotactic segmental per-cent, isotaxy segment and atactic segmental per-cent are called degree of syndiotacticity, degree of isotacticity and atactic degree.

Degree of syndiotacticity is the index of polymkeric substance three-dimensional regularity.

Value with tacticity in the middle of the present invention is the ratio (in molar percentage) of monomeric unit in the unit of all monomer derived that constitute polymkeric substance of expression syndiotaxy triad (triads).In this manual, term " triad " is meant one group of three continuous repeating unit in the polymkeric substance.One of configuration of the alpha-carbon (asymmetric carbon) of the carbonyl in every group of three repeating units is expressed as d, other configuration is expressed as 1, one group of continuous unit ddd or 111 is called isotactic triad so, one group of continuous unit dld or ldl are called the syndiotaxy triad, and one group of continuous unit ddl, lld, dll or ldd are called heterotactic triad.

Degree of syndiotacticity can be determined by nucleus magnetic resonance (NMR) spectrum.Particularly, polymer dissolution of the present invention or swelling in described polymkeric substance can the dissolved deuterated solvent, and are passed through ¹H NMR spectrography or ¹³C-NMR spectral detection sample.Determine to reflect respectively the signal integration value of degree of syndiotacticity, degree of isotacticity and atactic degree, and determine the ratio between them, can calculate degree of syndiotacticity thus.

Be dissolved at micro polymer of the present invention under the situation of deuterated solvent, as required, can be before use in it, add another part deuterated solvent or deuterated solvent not.Using under the situation of deuterated solvent not, preferred select to comprise NMR is analyzed the solvent that not have atom that influences.The example of this solvent comprises heavy chloroform (heavy chloroform) and heavy benzol, and it is right ¹The H-NMR spectroscopic data is influence not.

Incidentally, according to the spectrogram of polymkeric substance, can suitably change the selection of the nuclear that will in NMR spectrum, detect.Basically, based on ¹The analysis of H-NMR spectrographic is preferred. ¹Necessary peak in the H-NMR data and unnecessary peak overlapping or usefulness ¹Under the non-detectable situation of H-NMR spectrography, the preferred use ¹³C-NMR spectrum.

For example, in the substituent X that is connected with the alpha-carbon of carbonyl in (methyl) vinyl acrylate monomer is under the situation of hydrogen atom or methyl, between the hydrogen atom in hydrogen atom in the syndiotaxy triad, the hydrogen atom in the isotactic triad and the atactic triad, owing to X's ¹The chemical shift difference of H-NMR signal.Utilize this phenomenon to determine area ratio between these signals, can determine the ratio (rr/mr/mm) of syndiotaxy triad (rr)/atactic (be also referred to as assorted with) triad (mr)/isotactic triad (mm) thus.

For pointing out in the NMR spectrum, can be with reference to Shinpan K ō bunshi Bunseki HandoBukku, compied by The Japan Society for Analytical Chemistry (1995) and Mackromol.Chem., Rapid.Comrnun., 14,719 (1993).

In addition, be under the situation of fluorine atom or trifluoromethyl at the substituting group that is connected with the alpha-carbon of carbonyl in (methyl) vinyl acrylate monomer, can from ¹³The peak-to-peak area of C NMR is than definite degree of syndiotacticity.

That is to say, utilize following phenomenon to determine these peak-to-peak area ratios, can determine (rr/mr/mm) thus, described phenomenon is: between the carbon atom in the carbon atom in the syndiotaxy triad, the carbon atom in the isotactic triad and the atactic triad, be attributable to the alpha-carbon of carbonyl ¹³C NMR signal difference.

In the present invention, degree of syndiotacticity is the value that calculates from the tacticity of so determining, and is expressed as [rr/ (rr+mr+mm)] * 100 (%).This degree of syndiotacticity (rr) of the polymkeric substance that is obtained by the inventive method is high to 70% or higher.Therefore, this polymkeric substance is better than nonstereospecific polymer in thermotolerance and intensity.Degree of syndiotacticity is high more, these improvement in performance many more.

With the polymer phase ratio that uses up to now, polymkeric substance of the present invention has the better material performance on thermotolerance and intensity.The number-average molecular weight of polymkeric substance of the present invention is 2,000 or higher.Because from the angle of intensity and material property, high molecular is required, so the molecular weight of polymkeric substance is preferably 20,000 or higher.Usually, the molecular weight of this polymkeric substance is desirably 500,000 or lower.

When using radiation exposure, having specific refractory power that the light refractive index modulation polymer of the present invention of above-mentioned structure should present, to increase (Δ n) be 0.005 or more, is preferably 0.01 or more.As long as acquisition 0.005 or bigger refractive index difference, this polymkeric substance is applicable to optics, for example optical fiber and optical diffraction gratings.In this irradiation, to use under for example ultraviolet situation, irradiation dose is desirably 10J/cm ²Or still less, be preferably 5J/cm ²Or still less.Surpass 10J/cm when using ²Dosage uviolizing polymkeric substance the time, the situation of existence is, film flavescence, and have the transparency of infringement or the alteration of form of film (contraction) gradually.

In the present invention, can as required so-called light trigger (it produces the free radical material under the effect of light) be mixed in the light refractive index modulation polymer.Also sensitizer can be mixed, as the light trigger auxiliary agent.In addition, can mix chain-transfer agent.By mixing described light trigger, sensitizer or chain-transfer agent, reactivity is improved when vinyl side chain crosslinked, and makes that the change (increase) of specific refractory power is more satisfactory.

Can use light trigger, sensitizer or chain-transfer agent arbitrarily according to purpose.For example, showing the example that absorbs and produce the light trigger of free radical in the ultraviolet region comprises: hydrogen is captured type (hydrogenabstraction type) initiator, for example benzophenone cpd, aceotphenone compound and thioxanthone compound; With intramolecularly breaking type initiator, for example bitter almond oil camphor compound and alkyl phenyl ketone compound [reference: Hikari K ō ka Gijutsu Jit.suy ō Gaido, (Technonet Co., Ltd.), 2002].

The example of sensitizer (light trigger auxiliary agent) comprising: amine compound, for example trolamine and tri-isopropanolamine; And aminocompound, for example 4-dimethyl ethyl aminobenzoate.Yet sensitizer should not be construed as and is confined to these.[reference: Shigai-sen K ō ka Shistem (Sogo Gijutsu Center) 1990).

At United States Patent (USP) 3,652, in 275, discussed being used in combination of chain-transfer agent and light trigger to the effective effect of photocuring system.

The example of this chain-transfer agent comprises and is selected from the following compound those, described compound is trimethylolpropane tris-3-mercaptopropionic acid ester, N-phenylglycine, 1,1-dimethyl-3,5-diketo tetrahydrobenzene, 2-mercaptobenzothiazole, 2-sulfydryl benzoxazol, 2-mercaptobenzimidazole, tetramethylolmethane four (mercaptoacetate), 4-kharophen thiophenol, mercaptosuccinic acid, 12 carbon alkanethiols, beta-mercaptoethanol, mistabrom, 1-phenyl-4H-tetrazolium-5-mercaptan, the Ismipur mono-hydrate, two (5-sulfydryls-1,3,4-thio biphosphole-2-base, 2-sulfydryl-5-nitrobenzimidazole, 2-sulfydryl-4-sulfo group-6-chlorine benzoxazol etc.From with the angle of the suitability of the consistency of this polymkeric substance, reaction acceleration characteristics and general-use, particularly preferred compound is 2-sulfydryl benzoxazol (2-MBO), 2-mercaptobenzimidazole (2-MBI), 2-mercaptobenzothiazole (2-MBT), trimethylolpropane tris-3-mercaptopropionic acid ester etc.

In the present invention, the specific refractory power increase that produces as ray at the light of ultraviolet region by main is described.Yet, can suppose from the principle that specific refractory power increases, absorb and can excite the combination of the sensitizer of initiator or chain-transfer agent the time, when utilizing to show even also expect the increase of specific refractory power at non-ultraviolet zone (for example, visible region) in light wavelength.

As mentioned above, the ray except that ultraviolet ray, for example α-ray, beta-rays, gamma-radiation, neutron beam, electron beam etc. are also in the present invention available.

And the pending material of the present invention is not limited to following polymkeric substance, and described polymkeric substance is when using separately, and as above-mentioned light refractive index modulation polymer, experience 0.005 or bigger specific refractory power increase (Δ n).Also can use and wherein be mixed with light refractive index modulation polymer composition at least a in above-mentioned light trigger, sensitizer and the chain-transfer agent, realize purpose of the present invention.

In this composition, under ultraviolet situation for example, for obtain by irradiation 0.005 or the specific refractory power of bigger (being preferably 0.01 or bigger) increase (Δ n), the irradiation dose of ray is desirably 10J/cm ²Or still less, be preferably 5J/cm ²Or it is littler.

Embodiment

Below will provide embodiments of the invention, wherein use PVMA, be that homopolymer (embodiment 1), methacrylic vinyl acetate and another monomeric random copolymers (embodiment 2-4) of methacrylic vinyl acetate and methacrylic vinyl acetate and another monomeric segmented copolymer (embodiment 8 and 9) are as polymkeric substance.And with the composition of these light refractive index modulation polymers of uviolizing or described polymkeric substance, to increase their specific refractory power.

Below give embodiment (embodiment 5-7), wherein use PVMA, and in nitrogen atmosphere, carry out uviolizing as polymkeric substance.In addition, for purpose relatively, give the embodiment (comparative example 1) that wherein gathers (methyl methacrylate) with uviolizing.

Embodiment 1

(synthetic catalyst)

Synthetic anionic polycomplexation catalysts in the following manner.

Atmosphere in it is introduced 3.9616 gram SmI by in 1 liter of flask of argon replaces ₂With the 330mL tetrahydrofuran (THF).Under agitation, add 45.858 gram pentamethyl-cyclopentadienyl sylvite [(C in it ₅Me ₅) K].At room temperature react this mixture., under reduced pressure remove THF, and toluene is added in the residual solid material thereafter.Supernatant liquor reclaims, and carries out vacuum-drying.Then, use THF and hexane to [(C ₅Me ₅) ₂Sm (THF) ₂) carry out recrystallization.Should [(C with 2.5g ₅Me ₅) ₂Sm (THF) ₂] be dissolved in the 60mL toluene.In it, add the 2.2mL triethyl aluminum.Under agitation, react this mixture.Remove the throw out of generation, carry out recrystallization then, obtain (C ₅Me ₅) ₂SmMe (THF).

(synthetic PVMA)

Thorough drying and the introducing of deflated 80mL toluene have fully been removed in the Schlenk pipe of water and air.In it, add and used CaH ₂Dry mistake, the 20mL (18.7g of distillation purifying then; 166.4mmol) the methacrylic vinyl acetate.After internal temperature being adjusted to-78 ℃, will dilute (the C of 0.189g (0.373mmol) with the 5mL dry toluene ₅Me ₅) ₂The diluent that SmMe (THF) (it is an aforesaid method synthetic catalyzer) obtains is introduced in the Schienk pipe, with initiated polymerization.This catalyst consumption is for making that the ratio of monomer/catalyst is 446, and theoretical molecular is set to about 50,000.This reaction mixture of reaction is 3 hours under-78 ℃ polymerization temperature., methyl alcohol added in this reactive system, to end polyreaction thereafter.Further add methyl alcohol, with the polymkeric substance (poly-(methacrylic vinyl acetate)) of precipitation generation.Isolating polymer is dissolved in the ethyl acetate, carries out purifying with the methyl alcohol redeposition.

This polymkeric substance of vacuum-drying.The amount of the polymkeric substance that generates is 18.7g (productive rate＞99 weight %).Record its number-average molecular weight (Mn) and weight-average molecular weight (Mw) is respectively 77,000 and 115,000 by GPC (gel infiltration coloured light spectrometry), and its molecular weight distribution (Mw/Mn) is 1.49.In addition, according to ¹H-NMR spectrum determines that the per-cent [residual vinyl per-cent (%)=vinyl (4.9ppm)/methyl (1.3-0.6ppm) * 100] of the vinyl side chain of free redical polymerization residual in the polymkeric substance is 100%, and the three-dimensional regularity of main chain is 92% in degree of syndiotacticity (rr).

Polymkeric substance (poly-(methacrylic vinyl acetate)) ¹H-NMR is illustrated among Fig. 1.What Fig. 2 showed is, ¹The part of H-NMR figure is amplified, and its expression main chain methyl also is used to calculate tacticity.In order to calculate tacticity, use at 1.2-0.9ppm[at 1.19ppm (mm), 1.07ppm (mr) is about 0.92ppm (rr)] integrated curve of the methyl of the main chain of poly-(the methacrylic vinyl acetate) that detect.

Then, about 0.1 gram poly-(methacrylic vinyl acetate) that so obtains (PVMA) is immersed in the 50mL ethyl acetate, and vibrate 2 days with this solvent.Coming together to be insoluble to the component of ethyl acetate, and thorough drying.With the weight of its weight, determine the ratio (gel content) of insoluble component thus divided by the whole polymkeric substance of before with acetic acid ethyl dissolution, measuring.Found that gel content is 0 weight %.

(preparation rayed sample)

In the 0.4mL ethyl acetate, add 0.1 gram PVMA.Stir this mixture, with this polymkeric substance of abundant dissolving.Then, in the clean room, utilize spin coater (trade name " Spin Coater 1H-DX " is made by MIKASA), this PVMA/ ethyl acetate solution to be applied on the silicon chip by spin coating.The spin coating condition comprises 2,000rpm and 2 seconds.Be adjusted to 80 ℃ hot-plate on dring silicon agreement that contracts a film or TV play to an actor or actress 4 minute, to remove desolvate thereafter.Further, the wafer of 50 ℃ of vacuum-drying spin coatings 5 hours, obtaining thickness on silicon chip was the PVMA film of about 7 μ m.In said process, use silicon chip, and do not experience any special clean in advance.

Then, with the PVMA film on the uviolizing silicon chip.In order to shine, use ultraviolet irradiation device CV-100-G[type of device title, make by Fusion DV Systems Japan K.K.] and metal halide lamp as light source.Metal halide lamp sends the light that wavelength is 250-450nm.Yet when detecting the ultraviolet absorption spectrum of PVMA in advance, this polymkeric substance absorbs in performance place of 280-300nm place owing to the vinyl side chain.Therefore, the irradiation of judging other wavelength does not exert an influence, and the unspecial wavelength filter that uses.

DV radiometer and the [trade name of power pack dose meter measuring device used with high energy; Prepare by Fusion DVSystems Japan K.K.) the measurement exposure intensity.In D-bulb, 55% work output, the irradiation distance of 25mm and the linear velocity of 2 meter per seconds, do not carry out uviolizing and use under the condition of wave filter.Under these conditions, the integration light quantity is 4.242J/cm ²The irradiance and the light quantity of each wavelength zone are shown in Table 1.

Table 1

The ultraviolet wavelength district	Irradiance (W/cm ²)	Light quantity (J/cm ²)
The ultraviolet wavelength district	Irradiance (W/cm ²)	Light quantity (J/cm ²)	UVA(320-390nm)	1.373	1.971
UVB(280-320nm)	0.725	0.962	UVA(320-390nm)	1.373	1.971
UVB(280-320nm)	0.725	0.962	UVC(250-260nm)	0.071	0.100
UVV(395-445nm)	0.861	1.209	UVC(250-260nm)	0.071	0.100
UVV(395-445nm)	0.861	1.209	The integration light quantity	-	4.242

About the time of each uviolizing, use He-Ne laser (wavelength, 633nm), measure the specific refractory power of PVMA film by the m-Line method (prism-coupled method) of TE (transverse electric) pattern (being parallel to the plane glazing polarising pattern of mould material) and TM (transverse magnetic) pattern (polarising pattern on perpendicular to the plane of mould material).The results are shown in the table 2.

Table 2

Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)
Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)	0	1.49510	-	1.49486	-
4.2	1.50399	0.00899	1.50505	0.01019	0	1.49510	-	1.49486	-
4.2	1.50399	0.00899	1.50505	0.01019	8.4	1.50599	0.01089	1.50609	0.01123

It is evident that from The above results the integration light quantity is 8.4J/cm ²Irradiation can increase specific refractory power, measured as the TE pattern, increase to 1.50599 (refractive index difference, 0.01089) from 1.49510.The refractive index difference of this acquisition is enough big for the application of optics.Double refraction in this sample (absolute value of TM-TE) is extremely low, is low to moderate 0.0001.

Then, use reflectometer/transilluminator type HR-100[device type title; By Murakaiui ColorResearch Laboratory Co., Ltd. makes], estimate with 8.4J/cm ²The transparency of the film that the integration light quantity was shone and turbidity.Found that the total light transmittance of the film of uviolizing and turbidity are respectively 92% and 3%.

Embodiment 2

(synthetic VMA and another monomeric random copolymers)

Use synthetic catalyzer among the embodiment 1, the random copolymers of synthesize methyl acrylic vinyl acetate (VMA) and methyl methacrylate (MMA).

Thorough drying and the introducing of deflated 50mL toluene have fully been removed in the Schlenk pipe of water and air.In it, add and used CaH ₂Dry mistake, the 7.5mL (7.0g of distillation purifying then; 62.4mmol) VMA and 7.5mL (7.0g; 70.1mmol) MMA.After internal temperature being adjusted to-78 ℃, will dilute (the C of 0.198g (0.390mmol) with the 5mL dry toluene ₅Me ₅) ₂SmMe (THF) (as catalyzer) and the diluent that obtains is introduced in the Schienk pipe is with initiated polymerization.This catalyst consumption is for making that the ratio of monomer/catalyst is 160 (VMA) and 180 (MMA), and theoretical molecular is set to about 36,000.This reaction mixture of reaction is 3 hours under-78 ℃ polymerization temperature., methyl alcohol added in this reactive system, to end polyreaction thereafter.Further add methyl alcohol, with the polymkeric substance of precipitation generation.Isolating polymer is dissolved in the ethyl acetate, carries out purifying with the methyl alcohol redeposition.The polymkeric substance (VMA/MMA random copolymers) that vacuum-drying obtains.

The VMA/MMA copolymerization ratio of this polymkeric substance (mole %) is 47: 53.The amount of the polymkeric substance that generates is 8.0g (productive rate, 57.1 weight %).Record its number-average molecular weight (Mn) and weight-average molecular weight (Mw) is respectively 35,900 and 43,600 by GPC, and its molecular weight distribution (Mw/Mn) is 1.44.In addition, according to ¹H-NMR spectrum determines that the per-cent [residual vinyl per-cent (%)=vinyl (4.9ppm)/methyl (1.3-0.6ppm) * 100] of the vinyl side chain of free redical polymerization residual in the polymkeric substance is 100%, and the three-dimensional regularity of main chain that comprises MMA is 90% in degree of syndiotacticity (rr).

Then, the about 0.1 gram polymkeric substance (VMA/MMA random copolymers) that so obtains is immersed in the 50mL ethyl acetate, and vibrate 2 days with this solvent.Coming together to be insoluble to the component of ethyl acetate, and thorough drying.With the weight of its weight, determine the ratio (gel content) of insoluble component thus divided by the whole polymkeric substance of before with acetic acid ethyl dissolution, measuring.Found that gel content is 0 weight %.

(preparation rayed sample)

In the VMA/MMA random copolymers, mix 2-methyl isophthalic acid-[4-(methylthio group) phenyl] 2-morpholino propane-1 (" Irgacure 907 " are made by Ciba-Geigy Ltd.) as light trigger, its amount is 1 weight % based on random copolymers.Mode with identical with embodiment 1 forms film at the bottom of the silicon wafer-based, measure the refraction index changing that is caused by uviolizing by m-Line method (prism-coupled method).Measuring result is shown in Table 3.

Table 3

Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)
Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)	0	1.49427	-	1.49440	-
4.2	1.50502	0.01075	1.50525	0.01085	0	1.49427	-	1.49440	-
4.2	1.50502	0.01075	1.50525	0.01085	8.4	1.50403	0.00976	1.50415	0.00975

The above results clearly illustrates that following content.In the embodiment 2 that uses the VMA/MMA random copolymers, the integration light quantity is 4.2J/cm ²Irradiation can increase specific refractory power, measured as the TE pattern, increase to 1.50502 (refractive index difference, 0.01075) from 1.49427.This refractive index difference is enough big for the application of optics.Produce refraction index changing and be 0.01 ultraviolet irradiating dose less than among the embodiment 1 for obtaining the required ultraviolet irradiating dose of refraction index changing much at one.Can effectively obtain refraction index changing with lower irradiance.Double refraction in this sample (absolute value of TM-TE) is extremely low, is low to moderate 0.00023.And, detect the total light transmittance and the turbidity of this film in the same manner as described above.Found that its total light transmittance and turbidity are respectively 92% and 3%.

Embodiment 3

(synthetic VMA and another monomeric random copolymers)

With the method identical with embodiment 2, carry out the synthetic of multipolymer, difference is: change monomer composition and make it by 10mL (83.2mmol) VMA and 2.8mL (16.64mmol) N ', N '-dimethylaminoethyl methacrylic ester (DMMA) constitutes, and respectively will be as (the C of catalyzer ₅Me ₅) ₂The amount of SmMe (THF) and toluene changes 0.095g (0.187mmol) and 51mL into.Therefore, obtain the VMA/DMMA random copolymers.

VMA/DMMA copolymerization ratio (molar percentage) is 83: 17 in this polymkeric substance.The amount of the polymkeric substance that generates is 5.45g (productive rate, 45.6 weight %).Record its number-average molecular weight (Mn) and weight-average molecular weight (Mw) is respectively 65,000 and 91,600 by GPC, and its molecular weight distribution (Mw/Mn) is 1.41.In addition, according to ¹H-NMR spectrum determines that the per-cent of the vinyl side chain of free redical polymerization residual in the polymkeric substance is 100%, and the three-dimensional regularity of main chain is 92% in degree of syndiotacticity (rr).In addition, in mode same as described above, detect the ratio (gel content) of the insoluble component of this polymkeric substance.Found that gel content is 0 weight %.

(preparation rayed sample)

Then,, use this VMA/DMMA random copolymers, form film as the rayed sample in the mode identical with embodiment 2.By m-Line method (prism-coupled method), detect the refraction index changing of the film that causes by uviolizing.Measuring result is shown in Table 4.

Table 4

Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)
Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)	0	1.49536	-	1.49542	-
4.2	1.50440	0.00904	1.50466	0.00924	0	1.49536	-	1.49542	-
4.2	1.50440	0.00904	1.50466	0.00924	8.4	1.50573	0.01037	1.50583	0.01041

The above results clearly illustrates that following content.In the embodiment 3 that uses the VMA/DMMA random copolymers, the integration light quantity is 8.4J/cm ²Uviolizing can increase specific refractory power (TE pattern), increase to 1.50537 (refractive index difference, 0.01037) from 1.49536.This refractive index difference is enough big for the application of optics.Double refraction in this sample (absolute value of TM-TE) is extremely low, is low to moderate 0.00010.And, detect the total light transmittance and the turbidity of this film in the same manner as described above.Found that its total light transmittance and turbidity are respectively 90% and 2%.

Embodiment 4

(synthetic VMA and another monomeric random copolymers)

With the method identical with embodiment 2, carry out the synthetic of multipolymer, difference is: change monomer composition and make it by 5mL (41.6mmol) VMA and the (trade name " LIGHT-ESTER FM-108 " of 5mL (15.59mmol) methacrylic acid perfluoro capryl ethyl ester, by Kyoeisha Chemical Co., Ltd. make) (being designated hereinafter simply as PFMA) formation, and respectively will be as (the C of catalyzer ₅Me ₅) ₂The amount of SmMe (THF) and toluene changes 0.095g (0.187mmol) and 40mL into.Therefore, obtain the VMA/PFMA random copolymers.

VMA/PFMA copolymerization ratio (molar percentage) is 73: 27 in this polymkeric substance.The amount of the polymkeric substance that generates is 2.81g (productive rate, 21.7 weight %).Record its number-average molecular weight (Mn) and weight-average molecular weight (Mw) is respectively 41,900 and 56,200 by GPC, and its molecular weight distribution (Mw/Mn) is 1.34.In addition, according to ¹H-NMR spectrum determines that the per-cent of the vinyl side chain of free redical polymerization residual in the polymkeric substance is 100%, and the three-dimensional regularity of main chain is 90% in degree of syndiotacticity (rr).In addition, in mode same as described above, detect the ratio (gel content) of the insoluble component of this polymkeric substance.Found that gel content is 0 weight %.

(preparation rayed sample)

Then,, use this VMA/PFMA random copolymers, form film as the rayed sample in the mode identical with embodiment 2.By m-Line method (prism-coupled method), detect the refraction index changing of the film that causes by uviolizing.Measuring result is shown in Table 5.

Table 5

Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)
Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)	0	1.47425	-	1.47492	-
4.2	1.48630	0.01205	1.48656	0.01164	0	1.47425	-	1.47492	-
4.2	1.48630	0.01205	1.48656	0.01164	8.4	1.48304	0.00879	1.48334	0.00842

The above results clearly illustrates that following content.In the embodiment 4 that uses the VMA/PFMA random copolymers, the integration light quantity is 8.4J/cm ²Uviolizing can increase specific refractory power (TE pattern), increase to 1.48304 (refractive index difference, 0.00879) from 1.47425.This refractive index difference is enough big for the application of optics.Double refraction in this sample (absolute value of TM-TE) is extremely low, is low to moderate 0.00030.And, detect the total light transmittance and the turbidity of this film in the same manner as described above.Found that its total light transmittance and turbidity are respectively 90% and 3%.

Embodiment 5

With in advance by 2-methyl-[4-(methylthio group) phenyl]-2-morpholino propane-1 (" Irgacure 907 " as 1 weight % of light trigger, by Ciba-Geigy Ltd. preparation) be dissolved in the ethyl acetate and the solution of preparation adds and obtains among the PVMA among the embodiment 1, add-on is calculated as 1 weight % with the solid basis, based on PVMA.Form film in the mode identical as the rayed sample with embodiment 1.In the mode identical with embodiment 1, detect the refraction index changing of this film, difference is: carry out uviolizing in nitrogen atmosphere.Measuring result is shown among table 6 and Fig. 3.

Table 6

Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)
Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)	0	1.49325	-	1.49291	-
0.050	1.49986	0.00661	1.50015	0.00724	0	1.49325	-	1.49291	-
0.050	1.49986	0.00661	1.50015	0.00724	0.100	1.49906	0.00581	1.49879	0.00588
0.200	1.49925	0.00600	1.49694	0.00403	0.100	1.49906	0.00581	1.49879	0.00588
0.200	1.49925	0.00600	1.49694	0.00403	0.500	1.50288	0.00963	1.50347	0.01056
0.750	1.50242	0.00917	1.50375	0.01084	0.500	1.50288	0.00963	1.50347	0.01056
0.750	1.50242	0.00917	1.50375	0.01084	1.000	1.50319	0.00994	1.50372	0.01081
2.000	1.50294	0.00969	1.50381	0.01090	1.000	1.50319	0.00994	1.50372	0.01081
2.000	1.50294	0.00969	1.50381	0.01090	4.000	1.50271	0.00946	1.50315	0.01024

The above results clearly illustrates that following content.Light trigger is arranged and carry out in nitrogen atmosphere among the embodiment 5 of uviolizing in adding, the integration light quantity is 0.5J/cm ²Uviolizing can increase specific refractory power (TE pattern), increase to 1.50288 (refractive index difference, 0.00963) from 1.49325.This refractive index difference is enough big for the application of optics.The ultraviolet irradiating dose that produces this refraction index changing less than among the embodiment 1 for to obtain the required ultraviolet irradiating dose of refraction index changing much at one, in embodiment 1, do not use many nitrogen atmospheres.Can effectively obtain refraction index changing with lower irradiance.Double refraction in this sample (absolute value of TM-TE) is extremely low, is low to moderate 0.00059.

Embodiment 6

In the mode identical with embodiment 5, form film as the rayed sample, difference is: add 0.001g (1 weight %) 2-mercaptobenzothiazole as chain-transfer agent.In the mode identical, in nitrogen atmosphere,, and detect the refraction index changing of this film with this film of uviolizing with embodiment 5.Measuring result is shown among table 7 and Fig. 3.

Embodiment 7

In the mode identical with embodiment 5, form film as the rayed sample, difference is: add 0.001g (1 weight %) trimethylolpropane tris-3-mercaptopropionic acid ester as chain-transfer agent.In the mode identical, in nitrogen atmosphere,, and detect the refraction index changing of this film with this film of uviolizing with embodiment 5.Measuring result is shown among table 8 and Fig. 3.

Table 7

Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)
Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)	0	1.49355	-	1.49374	-
0.050	1.49701	0.00346	1.49762	0.00388	0	1.49355	-	1.49374	-
0.050	1.49701	0.00346	1.49762	0.00388	0.100	1.50019	0.00664	1.50106	0.00732
0.200	1.50695	0.01340	1.50759	0.01385	0.100	1.50019	0.00664	1.50106	0.00732
0.200	1.50695	0.01340	1.50759	0.01385	0.500	1.50654	0.01299	1.50631	0.01257
0.750	1.50625	0.01270	1.50621	0.01247	0.500	1.50654	0.01299	1.50631	0.01257
0.750	1.50625	0.01270	1.50621	0.01247	1.000	1.50550	0.01195	1.50501	0.01127
2.000	1.50547	0.01192	1.50578	0.01204	1.000	1.50550	0.01195	1.50501	0.01127
2.000	1.50547	0.01192	1.50578	0.01204	4.000	1.50633	0.01278	1.50646	0.01272

Table 8

Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)
Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)	0	1.49245	-	1.49261	-
0.050	1.49977	0.00732	1.49981	0.00720	0	1.49245	-	1.49261	-
0.050	1.49977	0.00732	1.49981	0.00720	0.100	1.50413	0.01168	1.50421	0.01160
0.200	1.50787	0.01542	1.50769	0.01508	0.100	1.50413	0.01168	1.50421	0.01160
0.200	1.50787	0.01542	1.50769	0.01508	0.500	1.50845	0.01600	1.50882	0.01621
0.750	1.50842	0.01597	1.50862	0.01601	0.500	1.50845	0.01600	1.50882	0.01621

1.000	1.50728	0.01483	1.50745	0.01484
1.000	1.50728	0.01483	1.50745	0.01484	2.000	1.50807	0.01562	1.50832	0.01571
4.000	1.50823	0.01578	1.50833	0.01572	2.000	1.50807	0.01562	1.50832	0.01571

The above results clearly illustrates that following content.In the embodiment 6 that adds embodiment 6 that chain-transfer agent is arranged and 7 in PVMA, the integration light quantity is 0.5J/cm ²Uviolizing can increase specific refractory power (TE pattern), increase to 1.50654 (refractive index difference, 0.01299) from 1.49355.In embodiment 7, the integration light quantity is 0.5J/cm ²Uviolizing can increase specific refractory power (TE pattern), increase to 1.50845 (refractive index difference, 0.01600) from 1.49245.These refractive index differences all are enough big for the application of optics.These refraction index changings are greater than the refraction index changing among the embodiment 5 that does not add chain-transfer agent.Can effectively obtain refraction index changing with lower irradiance.In these samples, double refraction (absolute value of TM-TE) is extremely low, and the double refraction of embodiment 6 is low to moderate 0.00023; The double refraction of embodiment 7 is low to moderate 0.00037.

Embodiment 8

(synthetic VMA and another monomeric segmented copolymer)

Use synthetic catalyzer among the embodiment 1, the segmented copolymer of synthetic VMA and MMA.

Thorough drying and the introducing of deflated 50mL toluene have fully been removed in the Schlenk pipe of water and air.In it, add and used CaH ₂Dry mistake, the 7.5mL (7.0g of distillation purifying then; 7.01mmol) MMA (methyl methacrylate).After internal temperature being adjusted to-78 ℃, will dilute (the C of 0.198g (0.390mmol) with the 5mL dry toluene ₅Me ₅) ₂SmMe (THF) (as catalyzer) and the diluent that obtains is introduced in the Schienk pipe is with initiated polymerization.This catalyst consumption is for making that the ratio of monomer/catalyst is 160 (VMA) and 180 (MMA), and theoretical molecular is set to about 36,000.This reaction mixture of reaction is 3 hours under-78 ℃ polymerization temperature.Thereafter, CaH has been used in adding in it ₂Dry mistake, the 7.5mL (7.0g of distillation purifying then; 62.4mmol) VMA (methacrylic vinyl acetate), under-78 ℃, carried out polyreaction again 5 hours.Methyl alcohol is added in this reactive system, to end polyreaction.Further add methyl alcohol, with the polymkeric substance of precipitation generation.Isolating polymer is dissolved in the ethyl acetate, carries out purifying with the methyl alcohol redeposition.

The polymkeric substance (VMA/MMA segmented copolymer) that vacuum-drying obtains.The VMA/MMA copolymerization ratio of this block polymer (mole %) is 47: 53.The amount of the polymkeric substance that generates is 13.4g (productive rate, 95.6 weight %).Record its number-average molecular weight (Mn) and weight-average molecular weight (Mw) is respectively 35,900 and 43,600 by GPC, and its molecular weight distribution (Mw/Mn) is 1.44.In addition, according to ¹H-NMR spectrum determines that the per-cent of the vinyl side chain of free redical polymerization residual in the polymkeric substance is 100%, and the three-dimensional regularity of main chain that comprises MMA is 90% in degree of syndiotacticity (rr).In addition, in the same manner as described above, detect the ratio (gel content) of insoluble component in this polymkeric substance.Found that gel content is 0 weight %.

(preparation rayed sample)

Then, in this VMA/MMA segmented copolymer, mix " Irgacure 907 " (being made by Ciba-GeigyLtd.) as light trigger, its amount is 1 weight % based on multipolymer.Mode with identical with embodiment 1 forms film at the bottom of the silicon wafer-based.By m-Line method (prism-coupled method), detect the refraction index changing of the film that causes by uviolizing.Measuring result is shown in Table 9.

Table 9

Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)
Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)	0	1.49406	-	1.49422	-
4.2	1.49813	0.00407	1.49833	0.00411	0	1.49406	-	1.49422	-
4.2	1.49813	0.00407	1.49833	0.00411	8.4	1.50054	0.00648	1.50078	0.00656

The above results clearly illustrates that following content.In the embodiment 8 that uses the VMA/MMA segmented copolymer, the integration light quantity is 8.4J/cm ²Irradiation can increase specific refractory power (TE pattern), increase to 1.50054 (refractive index difference, 0.00648) from 1.49406.This refractive index difference is enough big for the application of optics.Double refraction in this sample (absolute value of TM-TE) is extremely low, is low to moderate 0.00024.And, detect the total light transmittance and the turbidity of this film in the same manner as described above.Found that its total light transmittance and turbidity are respectively 89% and 3%.

Embodiment 9

(synthetic VMA and another monomeric segmented copolymer)

With the method identical with embodiment 8, carry out the synthetic of multipolymer, difference is: use methacrylic acid perfluoro capryl ethyl ester (above-mentioned PFMA, identical with described in the embodiment 4) replace MMA, and change monomer composition it is made of 5mL (41.6mmol) VMA and 5mL (15.59mmol) methacrylic acid perfluoro capryl ethyl ester (PFMA), and will introduce the toluene of Schlenk pipe respectively and as (the C of catalyzer ₅Me ₅) ₂The amount of SmMe (THF) changes 90mL and 0.095g (0.187mmol) into.Therefore, obtain the VMA/PFMA segmented copolymer.

VMA/PFMA copolymerization ratio (molar percentage) is 73: 27 in this block polymer.The amount of the polymkeric substance that generates is 3.20g (productive rate, 24.7 weight %).Record its number-average molecular weight (Mn) and weight-average molecular weight (Mw) is respectively 36,900 and 28,300 by GPC, and its molecular weight distribution (Mw/Mn) is 1.30.In addition, according to ¹H-NMR spectrum determines that the per-cent of the vinyl side chain of free redical polymerization residual in the polymkeric substance is 100%, and the three-dimensional regularity of main chain is 91% in degree of syndiotacticity (rr).In addition, in mode same as described above, detect the ratio (gel content) of the insoluble component of this polymkeric substance.Found that gel content is 0 weight %.

(preparation rayed sample)

Then,, use this VMA/PFMA segmented copolymer, form film as the rayed sample in the mode identical with embodiment 8.By m-Line method (prism-coupled method), detect the refraction index changing of the film that causes by uviolizing.Measuring result is shown in Table 10.

Table 10

Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)
Integration light quantity (J/cm ²)	The TE pattern	Δ n (refractive index difference)	The TM pattern	Δ n (refractive index difference)	0	1.46621	-	1.46615
4.2	1.46913	0.00292	1.46903	0.00288	0	1.46621	-	1.46615
4.2	1.46913	0.00292	1.46903	0.00288	8.4	1.47333	0.00712	1.47199	0.00584

The above results clearly illustrates that following content.In the embodiment 9 that uses the VMA/PFMA segmented copolymer, the integration light quantity is 8.4J/cm ²Uviolizing can increase specific refractory power (TE pattern), increase to 1.47333 (refractive index difference, 0.00712) from 1.46621.This refractive index difference is enough big for the application of optics.Double refraction in this sample (absolute value of TM-TE) is extremely low, is low to moderate 0.00134.And, detect the total light transmittance and the turbidity of this film in the same manner as described above.Found that its total light transmittance and turbidity are respectively 88% and 3%.

Comparative example 1

In the mode identical, with (PMMA) film of (Lot TCR2105, by Wako Pure Chemical Industries, Ltd. makes) of uviolizing poly-(methyl methacrylate) with embodiment 1.The result is, even in order to 105J/cm ²Integration light quantity irradiation PMMA film, its specific refractory power changes hardly.In addition, the PMMA that lives through uviolizing is sampled, and analyze with IR and NMR spectrum.Found that this polymkeric substance makes density crosslinking reaction that changes and the reaction that polarization is increased hardly.

Although, describe the present invention in detail with reference to specific embodiments of the present invention, it should be apparent to those skilled in the art that under the situation of the spirit and scope of the present invention, can be in the present invention, carrying out various variations and modification.

The application introduces its full content at this, as a reference based on the Japanese patent application (application number 2004-274513) of Japanese patent application of submitting on October 3rd, 2003 (application number 2003-345537) and submission on September 22nd, 2004.

Industrial applicibility

According to light refractive index modulation polymer of the present invention (described polymer is the residual vinyl side chain that free redical polymerization is arranged in molecule) or light refractive index modulation polymer composition of the present invention, the ray of available proper irradiation dosage (for example ultraviolet ray) shines the mechanograph of this polymer or composition, increase arbitrarily the refractive index of this mechanograph, and need not be by complicated step, for example as preoxidized step in the related art.

Claims

1. a light refractive index modulation polymer is characterized in that described polymkeric substance is to comprise the vinylformic acid vinyl monomer of following general formula (1) expression one or more polymer of monomers as neccessary composition,

CH ₂＝C(R ¹)C(＝O)O-R ²＝CH ₂ (1)

(R wherein ¹Be hydrogen atom or methyl, R ²For having the saturated or unsaturated alkyl of 1-20 carbon atom, this monomer can have one or more heteroatomss and/or one or more halogen atom in molecule), and

Wherein said polymkeric substance is the residual vinyl side chain that free redical polymerization is arranged in molecule, and

It is 0.005 or bigger (the m-Line method with the TE pattern is measured) behind pre-irradiation that the specific refractory power of this polymkeric substance when useful to irradiation of rays increases (Δ n).

2. the light refractive index modulation polymer of claim 1, wherein residual in the molecule have 90% or the vinyl side chain of higher free redical polymerization.

3. claim 1 or 2 light refractive index modulation polymer, described polymkeric substance is one of following polymkeric substance: (a) homopolymer of the vinylformic acid vinyl monomer of general formula (1) expression; (b) multipolymer of the vinylformic acid vinyl monomer of two or more general formulas (1) expression; (c) the vinylformic acid vinyl monomer of one or more general formulas (1) expressions and one or more other monomeric multipolymer.

4. each light refractive index modulation polymer among the claim 1-3, the three-dimensional regularity of wherein said polymkeric substance is 70% or higher in degree of syndiotacticity (rr).

5. each light refractive index modulation polymer among the claim 1-4, wherein said ray are ultraviolet ray.

6. the light refractive index modulation polymer of claim 5 is ultraviolet in usefulness, with 10J/cm ²Or littler irradiation dose when irradiation, it is 0.005 or bigger (the m-Line method with the TE pattern is measured) behind pre-irradiation that the specific refractory power of described polymkeric substance increases (Δ n).

7. light refractive index modulation polymer composition, it is characterized in that described composition comprises among the claim 1-6 each light refractive index modulation polymer and is selected from least a in light trigger, sensitizer and the chain-transfer agent, it is 0.005 or bigger (the m-Line method with the TE pattern is measured) behind pre-irradiation that the specific refractory power of this polymkeric substance when useful to irradiation of rays increases (Δ n).

8. light refractive index modulation polymer composition, it is characterized in that described composition comprises following polymkeric substance and is selected from least a in light trigger, sensitizer and the chain-transfer agent, described polymkeric substance is to comprise the vinylformic acid vinyl monomer of following general formula (1) expression one or more polymer of monomers as neccessary composition

CH ₂＝C(R ¹)C(＝O)O-R ²＝CH ₂ (1)

(R wherein ¹Be hydrogen atom or methyl, R ²For having the saturated or unsaturated alkyl of 1-20 carbon atom, this monomer can have one or more heteroatomss and/or one or more halogen atom in molecule),

This polymkeric substance residual vinyl side chain that free redical polymerization is arranged in molecule wherein, and

9. the light refractive index modulation polymer composition of claim 8, wherein said polymkeric substance are residual in molecule 90% or the vinyl side chain of higher free redical polymerization.

10. claim 8 or 9 light refractive index modulation polymer composition, wherein said polymkeric substance is one of following polymkeric substance: (a) homopolymer of the vinylformic acid vinyl monomer of general formula (1) expression; (b) multipolymer of the vinylformic acid vinyl monomer of two or more general formulas (1) expression; (c) the vinylformic acid vinyl monomer of one or more general formulas (1) expressions and one or more other monomeric multipolymer.

11. each light refractive index modulation polymer composition among the claim 8-10, the three-dimensional regularity of wherein said polymkeric substance are 70% or higher in degree of syndiotacticity (rr).

12. each light refractive index modulation polymer composition among the claim 7-11, wherein said ray are ultraviolet ray.

13. the light refractive index modulation polymer composition of claim 12 is using ultraviolet ray, with 10J/cm ²Or littler irradiation dose when irradiation, it is 0.005 or bigger (the m-Line method with the TE pattern is measured) behind pre-irradiation that the specific refractory power of described composition increases (Δ n).

14. method of regulating specific refractory power, it is characterized in that with among the radiation exposure claim 1-6 each light refractive index modulation polymer or claim 7-13 in each light refractive index modulation polymer composition, thus by irradiation, making the specific refractory power of described polymkeric substance or composition increase (Δ n) is 0.005 or bigger (the m-Line method with the TE pattern is measured) behind pre-irradiation.

15. the method for the adjusting specific refractory power of claim 14, wherein said ray are ultraviolet ray.

16. the method for the adjusting specific refractory power of claim 15, wherein said ultraviolet irradiation dosage is 10J/cm ²Or still less.

17. a method for preparing light refractive index modulation polymer is characterized in that:

Use rare earth metal as the metal complex catalyst in active centre as polymerization initiator, make one or more monomer generation anionoid polymerizations, obtain among the claim 1-6 each light refractive index modulation polymer thus as the vinylformic acid vinyl monomer of comprising of neccessary composition of following general formula (1) expression

CH ₂＝C(R ¹)C(＝O)O-R ²＝CH ₂ (1)

18. the method for preparing light refractive index modulation polymer of claim 17, wherein said rare earth metal is the metal complex of following general formula (2) expression as the metal complex in active centre:

(Cp1)(Cp2)Mr-(R) _p·(L) _q (2)