JP2010065083A - Two-photon absorbing polymerizable composition and optical device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-photon absorbing polymerizable composition that can produce an optical device having a high refractive index with high sensitivity, to provide an optical device produced by photolithography using the two-photon absorbing polymerizable composition and to provide a method for manufacturing the optical device. <P>SOLUTION: The two-photon absorbing polymerizable composition includes (a) a polymerizable compound, (b) a polymer compound containing a dithiocarbamate group and (c) a two-photon absorbing compound. A photocuring method using the composition is provided. An optical device structure using the composition is provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a two-photon absorption polymerizable composition having a high refractive index and a property of curing when irradiated with light. Furthermore, the present invention relates to an optical device using the two-photon absorption polymerizable composition and a method for producing the same.

Optical lithography is useful as a method for producing various optical devices such as polymer optical waveguides, polymer optical fibers, optical display materials, diffraction gratings, photonic crystals, and microreactors. In photolithography, by scanning a photosensitive material with a laser with a small diameter, the initiator contained in the material shifts to an excited state at the laser irradiation site to cause a photochemical reaction, and the site is specifically cured, This is a technique for forming a pattern inside the photosensitive material.
Conventionally widely used photolithography is called one-photon lithography mainly utilizing one-photon absorption reaction. As this one-photon lithography, a laser lithography method using an argon ion laser or a He—Cd laser, which is most commonly used at present, is used, and it is mainly used for manufacturing a one-dimensional or two-dimensional element.

In recent years, a lithography method using a nonlinear optical phenomenon called two-photon absorption has been proposed.
Two-photon absorption is a phenomenon in which a compound is excited by absorbing two photons at the same time, that is, a phenomenon in which two photons are absorbed at the same time in an energy region where there is no absorption band of the compound and an electron transitions to an excited state. It is. Usually, a substance is excited by absorbing one photon having an energy corresponding to the excitation energy, and a photon having an energy less than this energy is not absorbed. However, when the intensity of light is very strong, two photons in which the sum of two photon energies corresponds to the excitation energy may be absorbed simultaneously (non-resonant two-photon absorption). If this property is utilized, a light reaction can be caused only within the focal point where light is narrowed down by a lens, and an arbitrary state in the space can be selected to create an excited state, for example, lithography.

The basic principle of such two-photon lithography using two-photon absorption is the same as that of laser lithography using the one-photon absorption reaction. However, two-photon lithography using a two-photon absorption reaction can cause a photochemical reaction only at a condensing point having the highest light density, taking advantage of the feature that the spatial resolution of non-resonant two-photon absorption is very high. That is, by causing a polymerization reaction (curing) in a very fine space, a fine three-dimensional structure can be created with high accuracy. Therefore, it can be said that the two-photon lithography is suitable for manufacturing a multidimensional element.
In particular, the accuracy of 1 μm is the limit in general one-photon absorption laser lithography, whereas the resin can be cured with an accuracy of 0.5 μm or less in two-photon lithography. Therefore, in recent years, two-photon lithography has attracted attention as a method for producing various optical devices.

As described above, non-resonant two-photon absorption is a phenomenon that can occur when the intensity of light is very strong, in other words, a phenomenon that is very unlikely. For example, two-photon absorption breakage that indicates the ease of two-photon absorption. The area is very small, about 1 GM (1 GM = 1 × 10 ⁻⁵⁰ cm ⁴ molecule ⁻¹ photon ⁻¹ ). Therefore, in various applications using non-resonant two-photon absorption, the sensitivity is extremely low, and thus a high-power laser light source is required, which is a great obstacle to using two-photon absorption.

In recent years, a two-photon lithography method using a compound that efficiently absorbs two-photons, that is, a compound having a relatively large two-photon absorption cross section—a two-photon absorption compound—and a photopolymerizable compound has been proposed.
For example, a two-photon absorption polymerization method using a photopolymerization initiator and a urethane acrylate compound (Non-Patent Document 1), or a two-photon absorption polymerization method using a fluorene dye and an allylamine polymerization initiator (non-photon absorption polymerization) Patent Document 2) has been proposed. Furthermore, in order to perform highly sensitive two-photon absorption polymerization, a method using a specific two-photon absorption compound having a relatively large two-photon absorption cross-section (Patent Document 1), a dye, and a photopolymerizable polymer A photocurable resin using an ester dendrimer as a compound (Patent Document 2) has been reported.

A cured product having a high refractive index increases the optical value of an organic polymer material because it gives great added value such as increasing the reflectance and diffraction efficiency in terms of physical properties and performance when manufacturing various optical devices. It is possible and it is highly expected in industrial use. Therefore, if a cured product having a higher refractive index, specifically, a high refractive index exceeding, for example, 1.6 (D line) can be obtained with high sensitivity, a higher performance optical display material, diffraction grating, It is expected that optical devices such as photonic crystals can be manufactured.
However, the photocurable resin composition used in the above-described two-photon lithography utilizing two-photon absorption is generally composed of a polyfunctional monomer or oligomer that causes a photochemical reaction and a polymerization initiator for initiating the photochemical reaction. The known polyfunctional monomers or oligomers that cause photochemical reactions are those having a refractive index of about 1.5 (D-line), and were obtained using a two-photon absorption reaction. The refractive index of the cured product remained at about 1.5.
JP 2003-73410 A JP 2003-327645 A S. Maruo et al. , Opt. Lett. 1997, Vol. 22, paragraph 132 K. D. Belfield et al. , J .; Am. Chem. Soc. 2000, 122, 1217

  As described above, the refractive index of the cured product obtained from the curable resin composition used in the conventionally proposed two-photon lithography is about 1.5, and cannot be said to be a cured product having a high refractive index. there were. There has been no report on a photocurable resin composition that uses an organic polymer material having a high refractive index and can perform two-photon lithography with high sensitivity.

  This invention is made | formed in view of said situation, Comprising: It aims at providing the two-photon absorption polymeric composition which can obtain a high refractive index optical device with high sensitivity. Furthermore, an object of the present invention is to provide an optical device obtained by photolithography using the above two-photon absorption polymerizable composition, and a method for producing the same.

  As a result of intensive studies to achieve the above object, the inventors of the present invention made a composition containing a polymerizable compound, a dithiocarbamate group-containing polymer compound and a two-photon absorption compound, and the composition contains two-photons. The present invention was completed by finding that the cured product obtained has a high refractive index and can form a cured product having a fine structure by irradiation with a laser beam that causes absorption.

That is, as a first aspect of the present invention, there is provided a two-photon absorption polymerizable composition comprising (a) a polymerizable compound, (b) a dithiocarbamate group-containing polymer compound and (c) a two-photon absorption compound. ,
As a second aspect, the two-photon absorption polymerization according to the first aspect, wherein the weight average molecular weight of the (b) dithiocarbamate group-containing polymer compound measured in terms of polystyrene by gel permeation chromatography is 500 to 200,000. Sex composition,
As a third aspect, the (b) two-photon absorption polymerizable composition according to the first aspect or the second aspect, wherein the dithiocarbamate group-containing polymer compound is a branched polymer,
As a fourth aspect, the two-photon absorption polymerizable composition according to the third aspect, wherein the (b) dithiocarbamate group-containing polymer compound is a branched polymer represented by the formula (1),

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or a carbon atom. Represents an arylalkyl group of formula 7 to 12, or R ² and R ³ may be bonded to each other to form a ring with a nitrogen atom, A ¹ represents formula (2) or formula (3), n is the number of repeating unit structures and represents an integer of 2 to 100,000.)

(In the formula, A ² has 1 to 3 carbon atoms which may contain an ether bond or an ester bond.
0 represents a linear, branched or cyclic alkylene group, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms. 1 to 20 alkoxy groups, nitro groups, hydroxyl groups, amino groups, carboxyl groups or cyano groups are represented. )
As a fifth aspect, the two-photon absorption polymerizable composition according to any one of the first aspect to the fourth aspect, in which the polymerizable compound (a) is a polymerizable compound having an ethylenically unsaturated bond,
As a sixth aspect, the two-photon absorption polymerizable composition according to any one of the first aspect to the fourth aspect, in which the polymerizable compound (a) is a polymerizable compound having a cationic polymerizable site,
As a seventh aspect, a varnish containing the two-photon absorption polymerizable composition according to any one of the first aspect to the sixth aspect,
As an eighth aspect, a thin film produced from the varnish described in the seventh aspect,
As a ninth aspect, the two-photon absorption polymerizable composition according to any one of the first to sixth aspects has a longer wavelength than the linear absorption band of the (c) two-photon absorption compound contained therein, And the photocuring method characterized by polymerizing the two-photon absorption polymerizable composition using multiphoton absorption of two or more photons induced by irradiating a laser beam having a wavelength having no linear absorption,
As a tenth aspect, the present invention relates to an optical device structure obtained by curing the two-photon absorption polymerizable composition according to any one of the first to sixth aspects by two-photon absorption polymerization.

The two-photon absorption polymerizable composition of the present invention has very high sensitivity, and does not require a high-power laser light source when performing two-photon absorption lithography.
Further, the composition of the present invention can obtain a cured product having a high refractive index by the two-photon absorption lithography, and can obtain a high-resolution and highly accurate shaped article with a resolution of 0.5 μm or less.

  According to the photocuring method of the present invention, a shaped article having a fine structure is obtained by using the same principle as that of conventional one-photon absorption laser lithography without using a high-power laser light source, a mask, a pattern, or the like. be able to.

  Furthermore, since the optical device structure of the present invention is a structure having very high accuracy and a high refractive index as described above, optical devices such as high-performance optical display materials, diffraction gratings, and photonic crystals are manufactured. It can be applied to.

  The two-photon absorption polymerizable composition of the present invention includes (a) a polymerizable compound, (b) a dithiocarbamate group-containing polymer compound and (c) a two-photon absorption compound, and further includes (d) a photopolymerization initiator. But it ’s okay. Hereinafter, each component will be described in detail.

[(A) Polymerizable compound]
The polymerizable compound in the present invention is not particularly limited as long as it is a compound having 1 or more, preferably 1 to 6 polymerizable sites in the molecule to be polymerized by the action of (c) the two-photon absorption compound described later. . In order to promote curing by photopolymerization, it is preferable to use a compound having 2 to 6 polymerizable sites in the molecule.
Examples of the compound having a polymerizable moiety include a compound having an ethylenically unsaturated bond which is a radical polymerizable moiety, or a vinyl ether structure, a vinyl thioether structure, an epoxy ring or an oxetane ring which is a cationic polymerizable moiety. Examples include compounds having a cyclic ether structure and the like.

The term “polymerizable compound” in the present invention means a compound that is not a so-called polymer substance. Therefore, it includes not only a narrowly-defined monomer compound but also a dimer, trimer, oligomer or reactive polymer.
In addition, it is preferable to use a low viscosity, a good solubility, and a low volatility as a polymeric compound used for this invention.
Hereinafter, although the specific example of a polymeric compound is given, it is not limited to these compounds.

Examples of the compound having an ethylenically unsaturated bond, which is a radical polymerizable moiety, include unsaturated carboxylic acids, ester compounds of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and alicyclic polyhydroxy compounds and unsaturated compounds. Ester compound with saturated carboxylic acid, ester compound of aromatic polyhydroxy compound and unsaturated carboxylic acid, aliphatic polyhydroxy compound, ester compound of alicyclic polyhydroxy compound and unsaturated carboxylic acid, aliphatic polyhydroxy compound And ester compounds obtained by esterification reaction of polyvalent hydroxy compounds such as aromatic polyhydroxy compounds with unsaturated carboxylic acids and polyvalent carboxylic acids, and amide compounds of aliphatic polyamine compounds and unsaturated carboxylic acids. .
Among these, an unsaturated carboxylic acid or an ester compound having 3 to 20 oxyalkylene groups having 2 to 6 carbon atoms among various ester compounds with the unsaturated carboxylic acid is mentioned. Here, the oxyalkylene group having 2 to 6 carbon atoms is an oxyethylene group, an oxypropylene group, an oxybutylene group or the like, and these groups may be substituted with a hydroxy group, a halogen or the like.

  Examples of the unsaturated carboxylic acid include 2-acryloyloxyethyl succinic acid and 2-acryloyloxyethyl phthalic acid. In addition, methacrylic acid ester compounds in which the acrylate portion of these acrylic acid ester compounds is replaced with methacrylates, similarly itaconic acid ester compounds in place of itaconate, crotonic acid ester compounds in place of crotonate, and maleic acid ester compounds in place of maleate And so on.

  Among the ester compounds of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, polymerizable compounds having 3 to 20 oxyalkylene groups having 2 to 6 carbon atoms include ethoxy-modified pentaerythritol tetraacrylate (average ethoxy addition). Examples include 2.4 mol and 4 mol), propoxy-modified pentaerythritol tetraacrylate (average propoxy addition amount includes 4 mol and 10 mol), dipentaerythritol pentaacrylate, dipentaerythritol hexa Examples thereof include acrylate, ethoxy-modified trimethylolpropane triacrylate (average ethoxy addition amount includes 3 mol and 6 mol), and acrylic acid adduct of propylene glycol diglycidyl ether. Other ester compounds of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include 2-hydroxy-3-phenoxypropyl acrylate, 3-chloro-2-hydroxypropyl acrylate, tripropylene glycol diacrylate, and trimethylolpropane. Alkylene glycol diacrylates such as triacrylate, trimethylolethane triacrylate, ditrimethylolpropane tetraacrylate, 1,6-hexanediol diacrylate, polybutanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate And acrylate compounds such as glycerol acrylate. In addition, methacrylic acid ester compounds in which the acrylate portion of these acrylic acid ester compounds is replaced with methacrylates, similarly itaconic acid ester compounds in place of itaconate, crotonic acid ester compounds in place of crotonate, and maleic acid ester compounds in place of maleate And so on.

  Among the ester compounds of the alicyclic polyhydroxy compound and the unsaturated carboxylic acid, the polymerizable compound having 3 to 20 oxyalkylene groups having 2 to 6 carbon atoms includes ethoxy-modified hydrogenated bisphenol A diacrylate ( The average ethoxy addition amount is 4 moles). Examples of ester compounds of other alicyclic polyhydroxy compounds and unsaturated carboxylic acids include tricyclodecane dimethanol diacrylate. In addition, methacrylic acid ester compounds in which the acrylate portion of these acrylic acid ester compounds is replaced with methacrylates, similarly itaconic acid ester compounds in place of itaconate, crotonic acid ester compounds in place of crotonate, and maleic acid ester compounds in place of maleate And so on.

Among the ester compounds of the aromatic polyhydroxy compound and the unsaturated carboxylic acid, the polymerizable compound having 3 to 20 oxyalkylene groups having 2 to 6 carbon atoms includes ethoxy-modified bisphenol A diacrylate (average ethoxy addition). 3 moles, 4 moles, 10 moles, 20 moles, etc.), propoxy modified bisphenol A diacrylate, ethoxy-propoxy modified bisphenol A diacrylate (average ethoxy, propoxy addition amount includes 18 moles, etc.) ), Ethoxy-modified bisphenol F diacrylate (the average ethoxy addition amount is 4 mol), propoxy-modified bisphenol F diacrylate, ethoxy-propoxy-modified bisphenol F diacrylate, and the like. Other ester compounds of aromatic polyhydroxy compounds and unsaturated carboxylic acids include bisphenol A diacrylate, bisphenol F diacrylate, hydroquinone diacrylate, resorcin diacrylate, and p-bis (β-acryloyloxyethylthio) xylylene. And pyrogallol triacrylate and the like, and ethoxy and propoxy-modified products thereof. In addition, methacrylic acid ester compounds in which the acrylate portion of these acrylic acid ester compounds is replaced with methacrylates, similarly itaconic acid ester compounds in place of itaconate, crotonic acid ester compounds in place of crotonate, and maleic acid ester compounds in place of maleate And so on.

  The ester compound obtained by the esterification reaction of a polyvalent hydroxy compound such as the aliphatic polyhydroxy compound and aromatic polyhydroxy compound with an unsaturated carboxylic acid and polyvalent carboxylic acid is not necessarily a single substance, but is representative. Specific examples include condensates of acrylic acid and phthalic acid and ethylene glycol, condensates of acrylic acid and maleic acid and diethylene glycol, condensates of acrylic acid and benzoic acid and trimethylolpropane, acrylic acid and terephthalic acid and pentane. Examples include condensates of erythritol and dipentaerythritol, and condensates of acrylic acid and adipic acid with butanediol and glycerin.

  Other examples of the compound having an ethylenically unsaturated bond used in the present invention include a urethane compound that can be obtained by a reaction between a polyvalent isocyanate and a hydroxyalkyl unsaturated carboxylic acid ester, a polyvalent epoxy compound, and a hydroxyalkyl. Mention may be made of compounds obtainable by reaction with unsaturated carboxylic acid esters, polyvalent acrylates and methacrylates having a phosphate group. Further, for example, acrylamide compounds such as ethylene-bisacrylamide, allyl ester compounds such as diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate are useful.

In the present invention, the compound having an ethylenically unsaturated bond is particularly preferably an acrylic ester compound or a methacrylic ester compound.
These compounds having an ethylenically unsaturated bond may be used alone or in combination of two or more as required.

  Examples of the polymerizable compound having a vinyl ether structure which is a cationically polymerizable site include vinyl-2-chloroethyl ether, vinyl normal butyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, Examples thereof include trimethylolethane trivinyl ether and vinyl glycidyl ether.

Examples of the polymerizable compound having an epoxy ring include diglycerol polydiglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, trimethylol. Propane polyglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tertiary butyl phenyl glycidyl ether, adipic acid diglycidyl ether, o-phthalic acid Diglycidyl ether, dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylol perful Rhohexanediglycidyl ether, 4,4′-bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexylmethyl-3 ′, 4'-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, 2- (3,4-epoxycyclohexyl) -3 ', 4'-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2- Ethylenedioxy-bis (3,4-epoxycyclohexylmethane), 4 ′, 5′-epoxy-2′-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis (3 4-epoxycyclohexanecarboxylate) Bis- (3,4-epoxycyclohexylmethyl) adipate, bis (2,3-epoxycyclopentyl) ether, and the like.

  Examples of the polymerizable compound having an oxetane ring include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3,3-diethyloxetane, and 3-ethyl-3- ( Compounds having one oxetane ring such as 2-ethylhexyloxymethyl) oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis (1-ethyl (3-oxetanyl) And compounds having two or more oxetane rings such as methyl ether and pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether.

  These polymerizable compounds may be used alone or in combination of two or more as required.

[(B) Dithiocarbamate group-containing polymer compound]
Examples of the polymer compound having a dithiocarbamate group used in the two-photon absorption polymerizable composition of the present invention include a branched polymer compound represented by the following formula (1) or the following formula (4). The linear polymer compound represented is mentioned.

In the above formula (1) or formula (4), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³
Each independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms, and R ² and R ³ are It may be bonded to form a ring with a nitrogen atom, and n is the number of repeating unit structures and represents an integer of 2 to 100,000.

Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a cyclopentyl group, and a normal pentyl group.
Examples of the hydroxyalkyl group having 1 to 5 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
Examples of the arylalkyl group having 7 to 12 carbon atoms include a benzyl group and a phenethyl group.

In addition, examples of the ring formed by combining R ² and R ³ together with the nitrogen atom bonded thereto include a 4- to 8-membered ring, and a ring containing 4 to 6 methylene groups as the ring. Moreover, the ring containing an oxygen atom or a sulfur atom, and four to six methylene groups is also mentioned.
Specific examples of the ring formed by combining R ² and R ³ together with the nitrogen atom bonded to them include a piperidine ring, a pyrrolidine ring, a morpholine ring, a thiomorpholine ring, and a homopiperidine ring.

In the above formula (1) or (4), A ¹ represents a structure represented by the following formula (2) or formula (3).

In the above formulas (2) and (3), A ² represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or an amino group. Represents a carboxyl group or a cyano group.

Specific examples of the linear alkylene group include a methylene group, an ethylene group, a normal propylene group, a normal butylene group, and a normal hexylene group. Specific examples of the branched alkylene group include isopropylene group, isobutylene group and 2-methylpropylene group.
Examples of the cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic or bridged cyclic structure having 3 to 30 carbon atoms. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, pentacyclo structure or the like having 4 or more carbon atoms. The structural examples (a) to (s) of the alicyclic moiety in the alicyclic aliphatic group are shown below.

Examples of the alkyl group having 1 to 20 carbon atoms in Y ¹ , Y ² , Y ³ and Y ⁴ include methyl group, ethyl group, isopropyl group, cyclohexyl group and normal pentyl group.
Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, isopropoxy group, cyclohexyloxy group, and normal pentyloxy group.
The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
Y ¹ , Y ² , Y ³ and Y ⁴ are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

The polymer compound having a dithiocarbamate group used in the present invention has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography of 500 to 5,000,000, preferably 1,000 to 1,000. 1,000, more preferably 2,000 to 500,000, and most preferably 3,000 to 200,000.
Further, the dispersity Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, 1.1 to 6.0, or 1.2 to 5.0. .

As will be described later, in the present invention, the above polymer compound having a dithiocarbamate group is used to form a two-photon absorption polymerizable composition, a photosensitive layer is formed using the composition, and photocured to form an optical device. Get a structure. At this time, in order to improve the workability in forming the photosensitive layer, that is, to improve the coating property of the composition on a support, the composition preferably has a low viscosity. Therefore, the polymer compound having a dithiocarbamate group contained in the composition is preferably a branched polymer compound, that is, a polymer compound represented by the formula (1).
The polymer compound having a dithiocarbamate group is, for example, Koji Ishizu, Akihide Mori, Polymer International 50, 906-910 (2001), Koji Ishizu, Takeshi Shibuya, Akihide Mori, 28 It can be produced by the method described in Ishizu, Yoshihiro Ohta, Journal of Materials Science Letters, 22 (9), 647-650 (2003).

[(C) Two-photon absorption compound]
The two-photon absorption compound in the present invention refers to a compound that efficiently absorbs two photons, that is, a compound having a relatively large two-photon absorption cross-sectional area, and a known compound can be used without particular limitation. When performing two-photon lithography, the two-photon absorbing compound absorbs two photons, and the excitation energy causes a photocrosslinking reaction between the polymerizable compound and the dithiocarbamate group-containing polymer compound, thereby generating a cured product.

  Examples of the two-photon absorption compound include the following (1) to (1) described in the Optical Application Technology / Material Encyclopedia (issue: Industrial Technology Service Center, Inc., issue date: April 26, 2006, page 483). 21) the two-photon absorption dye.

Or as a two-photon absorption compound, the general formula (1) described in JP-A-2003-73410;
X ² -(-CR ⁴ = CR ^3- ) _m -C (= O)-(-CR ¹ = CR ^2- ) _n -X ¹ (1)
(Wherein, X ¹ and X ² represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, which may be the same or different, and R ¹ , R ² , R ³ and R ⁴ are Each independently represents a hydrogen atom or a substituent, and some of R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a ring, and n and m are 2 or more The plurality of R ¹ , R ² , R ³ and R ⁴ may be the same or different, and n and m each independently represent an integer of 1 to 4.)
Examples thereof include compounds represented by compound numbers (1) to (140) in the same literature.
Further, examples of the two-photon absorption compound include the following compounds described in J. Mater. Chem., 2003, 13, 1575-1581.

  Two-photon absorption compounds may be used alone or in admixture of two or more as required.

[(D) Photopolymerization initiator]
In the present invention, in addition to the components (a) to (c), (d) a photopolymerizable initiator may be contained.
(D) The photopolymerization initiator is not particularly limited as long as it is a compound having a function of absorbing a wavelength in the ultraviolet region of 300 to 550 nm and initiating polymerization of the (a) polymerizable compound.
When the compound having an ethylenically unsaturated bond which is the radical polymerizable site is used as the polymerizable compound (a), a photo radical polymerization initiator that generates an active radical at the time of exposure is used as the photo polymerization initiator. preferable.
Further, when the compound having a vinyl ether structure, an epoxy ring or an oxetane ring, which is the cationic polymerizable site, is used as the polymerizable compound (a), a Lewis acid or Bronsted acid is used as a photopolymerization initiator at the time of exposure. Photoacid generators that generate are preferred.

The photo radical polymerization initiator is not particularly limited as long as it is a compound that generates an active radical at the time of exposure. For example, a benzoin compound, an α-aminoalkylphenone compound, a thioxanthone compound, an azo compound, an azide compound , Diazo compounds, o-quinonediazide compounds, acylphosphine oxide compounds, oxime ester compounds, organic peroxides, benzophenones, biscoumarins, bisimidazole compounds, titanocene compounds, thiol compounds, halogenated hydrocarbon compounds, trichloro Methyltriazine compounds or onium salt compounds such as iodonium salt compounds and sulfonium salt compounds are used.
A radical photopolymerization initiator may be used alone or in combination of two or more as required.

  The titanocene compound is not particularly limited, and specifically, dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-bisphenyl, dicyclopentadienyl-titanium-bis (2,3 , 4,5,6-pentafluorophenyl), dicyclopentadienyl-titanium-bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl-titanium-bis (2,4,6) -Trifluorophenyl), dicyclopentadienyl-titanium-bis (2,6-difluorophenyl), dicyclopentadienyl-titanium-bis (2,4-difluorophenyl), bis (methylcyclopentadienyl) -Titanium-bis (2,3,4,5,6-pentafluorophenyl), bis (methylcyclopentadienyl) -titanium-bis 2,3,5,6-tetrafluorophenyl), bis (methylcyclopentadienyl) -titanium-bis (2,6-difluorophenyl), and dicyclopentadienyl-titanium-bis (2,6-difluoro) -3- (1H-pyrrol-1-yl) -phenyl) and the like.

  Examples of benzoin compounds include benzoin ethyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropane. -1-one etc. can be mentioned.

Examples of α-aminoalkylphenone compounds include 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho And linophenyl) -butan-1-one.
Examples of the thioxanthone compound include thioxanthone, 1-chlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like.

  Examples of the acylphosphine oxide compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of oxime ester compounds include 1,2-octanedione-1- (4- (phenylthio) -2- (O-benzoyloxime)) and ethanone-1- (9-ethyl-6- (2-methylbenzoyl). And -9H-carbazol-3-yl) -1- (O-acetyloxime).

  Examples of the azide compounds include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4′-diazidochalcone, 4,4′-diazidodiphenyl sulfide, 2, Examples thereof include 6-bis (4′-azidobenzal) -4-methylcyclohexanone and α-cyano-4,4′-dibenzostilbene.

Examples of the azo compound include 2,2′-azobis (2-aminodipropane) hydrochloride, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis [N- (2-carboxyethyl). ) -2-methylpropionamidine], dimethyl 2,2′-azobisisobutyrate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis {2-methyl-N- [2- (1-hydroxybutyl) )] Propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2′-azobis [2- (5-methyl-2-imidazoline-2- Il) propane] Acid salt, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] sulfate, 2 , 2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] hydrochloride, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2- Imidazolin-2-yl] propane} hydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] and the like.

  Examples of the diazo compound include 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzeneborofluoride, 1-diazo-4-N, N-dimethylaminobenzene chloride, and 1-diazo-4-N. , N-diethylaminobenzeneborofluoride and the like.

  Examples of o-quinonediazide compounds include 1,2-naphthoquinonediazide (2) -4-sulfonic acid sodium salt, 1,2-naphthoquinonediazide (2) -5-sulfonic acid ester, and 1,2-naphthoquinonediazide (2 ) -4-sulfonyl chloride and the like.

  Examples of benzophenones include benzophenone, 4,4′-bisdiethylaminobenzophenone, 1,4-dibenzoylbenzene, 10-butyl-2-chloroacridone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, 3,3 ′, 4,4′-tetra (tertiary butyl peroxycarbonyl) benzophenone and the like can be mentioned.

Biscumarins include, for example, 3,3′-carbonylbis (7- (diethylamino) -2H-chromen-2-one) and the like, which is a product of BC (CAS [63226-13-1] manufactured by Midori Chemical Co., Ltd. ).
Examples of the bisimidazole compound include 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetrakis (3,4,5-trimethoxyphenyl) 1,2′-bisimidazole, and 2 , 2'-bis (o-chlorophenyl) 4,5,4 ', 5'-tetraphenyl-1,2'-bisimidazole and the like.

  The photoacid generator is not particularly limited as long as it is a compound that generates a Lewis acid or a Bronsted acid upon exposure. For example, an onium salt compound such as a diallyl iodonium salt compound, a triaryl sulfonate compound, or a diazonium salt compound , And iron arene complex compounds. A photo-acid generator may be used independently and may mix and use 2 or more types as needed.

Examples of the diallyliodonium salt compound include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-ditertiarybutyldiphenyliodonium, (4-methylphenyl) [4-
(2-methylpropyl) phenyl] iodonium, iodonium tetrafluoroborate such as 3,3′-dinitrophenyliodonium, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.

Examples of the triarylsulfonate compound include triphenylsulfonium, 4-tertiarybutyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-methoxyphenyl) sulfonium, and 4-thiophenyltriphenylsulfonium. And the like, such as tetrafluoroborate of sulfonium such as hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.

  Examples of the iron arene complex compound include biscyclopentadienyl- (η6-isopropylbenzene) -iron (II) hexafluorophosphate.

[Two-photon absorption polymerizable composition]
The two-photon absorption polymerizable composition of the present invention comprises (a) a polymerizable compound, (b) a dithiocarbamate group-containing polymer compound and (c) a two-photon absorption compound, and optionally (d) a photopolymerization initiator, These components (a) to (d) can be obtained by mixing at an arbitrary mixing ratio.
(A) The polymerizable compound is preferably used at a ratio of 1 to 100 parts by mass with respect to 100 parts by mass of the (b) dithiocarbamate group-containing polymer compound. (A) When the polymerizable compound exceeds 100 parts by mass, a high refractive index cannot be obtained, and when it is less than 1 part by mass, a long exposure time is required to obtain a sufficient cured product. .
(C) The two-photon absorption compound is preferably used at a ratio of 0.01 to 10 parts by mass with respect to 100 parts by mass of the (b) dithiocarbamate group-containing polymer compound. More preferably, it is used in proportions.
Further, when (d) a photopolymerization initiator is included, it is preferably used in a proportion of 0.01 to 10 parts by mass with respect to 100 parts by mass of the (b) dithiocarbamate group-containing polymer compound. More preferably, it is used at a ratio of 1 to 5 parts by mass.

In addition, the two-photon absorption polymerizable composition of the present invention can contain an organic solvent having sufficient solubility for the above components. Examples of organic solvents that can be used include cellosolv solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, Propylene glycol solvents such as propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl acetate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl Acetoacetate, methyl lactate, ethyl lactate, 3-methoxypropio Ester solvents such as methyl acid, alcohol solvents such as butanol, heptanol, hexanol, diacetone alcohol, furfuryl alcohol, ketone solvents such as methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, ether solvents such as tetrahydrofuran and dioxane Lactone solvents such as γ-butyllactone, highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, or mixed solvents thereof, These include those obtained by adding aromatic hydrocarbons such as toluene and xylene.
The proportion of these organic solvents used is usually in the range of about 0.1 to 10 times by mass ratio with respect to the total mass of the two-photon absorption polymerizable composition of the present invention.

  Further, the two-photon absorption polymerizable composition of the present invention contains various additives such as a binder, an antioxidant, a light stabilizer, a heat stabilizer, a sensitizer, a plasticizer, a lubricant, a chain transfer agent, or a dye. You may add as needed. The binder can be used for the purpose of adjusting the film formability and uniformity of the composition before photolithography.

The two-photon absorption polymerizable composition of the present invention can be formed on a support, for example, and dried as necessary to form a photosensitive layer. A suitable thickness of the photosensitive layer is, for example, about 1 to 1,000 μm. Subsequently, a support or a protective layer for blocking oxygen can be provided on the photosensitive layer. These support and protective layer need to be a transparent substance in order to transmit light because the photosensitive layer composed of the two-photon absorption polymerizable composition of the present invention undergoes exposure polymerization.

As the support, a transparent glass plate, an acrylic plate, a polyethylene terephthalate film, a polyethylene film, or the like is used. As the transparent resin film, a polyethylene terephthalate film, a polyethylene film, or the like is used. As a coating method, in addition to a direct dropping method, a conventionally known method such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating, and spin coating may be used. it can.
As the protective layer, a known technique for preventing adverse effects such as a decrease in sensitivity due to oxygen and deterioration in storage stability, for example, a water-soluble polymer can be applied and used.

In order to perform photolithography using the two-photon absorption polymerizable composition of the present invention, as described above, first, a thin film is formed by coating the composition on a suitable support such as a glass plate, Next, laser exposure is performed on the thin film. Further, after the laser exposure, the unreacted portion can be replaced with a resin having a different refractive index, for example, a photocurable resin composition.
As a laser light source, for example, an argon ion laser (458 nm, 488 nm, 514.5 nm), a krypton ion laser (647.1 nm), an Nd: YAG laser (532 nm), an Nd: YVO4 laser (532 nm), an InGaN laser (405 nm), A He—Cd laser (325 nm, 442 nm), a near infrared femtosecond Ti-sapphire laser (700 to 1,000 nm), a near infrared femtosecond fiber laser, or the like is used.
The preferred laser irradiation intensity varies depending on the optical device used. However, if the laser irradiation intensity is weak, curing is insufficient, the exposed portion becomes thin and weak, and may have a wavy shape. Further, when the intensity of laser irradiation is high, it is sufficiently cured and the exposed portion becomes firm, but it may be thicker than a desired size (thickness). In the system using the optical device shown in FIG. 1 used in Examples described later, the laser intensity in the immediate vicinity of the objective lens 7 is preferably 8 to 12 mW.

As described above, the two-photon absorption polymerizable composition of the present invention can be used for two-photon lithography. The two-photon lithography is capable of curing only a specific portion as compared with the one-photon lithography. In other words, the two-photon lithography is a more precise and highly integrated multidimensional element because a high-precision pattern can be formed. It can be used for the manufacture of optical devices.
Moreover, since the cured product (molded article) obtained from the two-photon absorption polymerizable composition of the present invention has a high refractive index, when used in various optical devices, it gives great added value in terms of materials and performance of the device. Can do.
Therefore, the two-photon absorption polymerizable compound of the present invention, the photocuring method using the photocomposition, and the optical device structure obtained from the composition are specifically polymer optical waveguide, polymer optical fiber, optical It can be effectively used for fine optical devices such as display materials, diffraction gratings, photonic crystals, and microreactors.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Reference Example 1: Synthesis of N, N-diethyldithiocarbamylmethylstyrene
In a 2 L reaction flask, chloromethylstyrene [manufactured by AGC Seimi Chemical Co., Ltd., CMS-14 (trade name)] 120 g, sodium N, N-diethyldithiocarbamate trihydrate [manufactured by Kanto Chemical Co., Ltd.] 181 g , 1400 g of acetone was charged, and 1 at 40 ° C. with stirring.
Reacted for hours. After the reaction, the precipitated sodium chloride was removed by filtration, and then acetone was distilled off from the reaction solution with an evaporator to obtain a reaction crude powder. This reaction crude powder was redissolved in toluene, and after separation in a toluene / water system, the target product was recrystallized from the toluene phase in a −20 ° C. freezer. The recrystallized product was filtered and vacuum-dried to obtain 206 g of the desired product as white powder (yield 97%). The purity (area percentage) by liquid chromatography was 100% (melting point 56 ° C.).

Reference Example 2: Synthesis of Styrenic Hyperbranched Polymer (HPS) Having Dithiocarbamate Group at Molecular Terminal>
A 300 mL reaction flask was charged with 108 g of N, N-diethyldithiocarbamylmethylstyrene and 72 g of toluene prepared in Reference Example 1 and stirred to prepare a pale yellow transparent solution, and then the inside of the reaction system was purged with nitrogen. A 100 W high-pressure mercury lamp (manufactured by Sen Special Light Source Co., Ltd., HL-100) was turned on from the middle of this solution, and a photopolymerization reaction by internal irradiation was performed at room temperature for 12 hours with stirring. Next, this reaction liquid was added to 3,000 g of methanol to reprecipitate the polymer in a highly viscous lump state, and then the supernatant liquid was removed by decantation. Furthermore, after this polymer was redissolved in 300 g of tetrahydrofuran, this solution was added to 3,000 g of methanol to reprecipitate the polymer in a slurry state. This slurry was filtered and vacuum-dried to obtain 48 g of the desired product as a white powder.

  The obtained target product (HPS) had a weight average molecular weight Mw of 20,900 and a dispersity Mw / Mn of 4.9 as measured by gel permeation chromatography in terms of polystyrene. The results of elemental analysis were carbon 64.6%, hydrogen 7.4%, nitrogen 5.0% and sulfur 25.3%. From the thermogravimetric analysis, the 5% weight loss temperature was 248 ° C. The obtained HPS has a structure represented by the formula (5) (refractive index at a wavelength of 589 nm (NaD line): 1.585).

Reference Example 3: Synthesis of N, N-diethyldithiocarbamylethyl methacrylate
A 2 L reaction flask was charged with 100 g of chloroethyl methacrylate [manufactured by Lancaster], 178 g of sodium N, N-diethyldithiocarbamate trihydrate [manufactured by Kanto Chemical Co., Ltd.], and 1,100 g of acetone. The reaction was carried out at ° C for 14 hours. After the reaction, the precipitated sodium chloride was removed by filtration, and then acetone was distilled off from the reaction solution with an evaporator to obtain a reaction crude powder. This reaction crude powder was redissolved in 1,2-dichloroethane, and after separation in a 1,2-dichloroethane / water system, 1,2-dichloroethane was distilled off from the 1,2-dichloroethane phase to give 171 g of the desired product as a yellow liquid. (Yield 97%) was obtained. The purity (area percentage) by liquid chromatography was 96%.

<Reference Example 4: Synthesis of acrylic hyperbranched polymer (HPEMA) having dithiocarbamate group at molecular end>
A 300 ml reaction flask was charged with 90 g of N, N-diethyldithiocarbamylethyl methacrylate and 90 g of toluene to prepare a pale yellow transparent solution by stirring, and then the inside of the reaction system was purged with nitrogen. A 100 W high-pressure mercury lamp (manufactured by Sen Special Light Source Co., Ltd., HL-100) was turned on from the middle of this solution, and a photopolymerization reaction by internal irradiation was performed at room temperature for 5 hours with stirring. Next, this reaction liquid was added to 3,000 g of methanol to reprecipitate the polymer in a highly viscous lump state, and then the supernatant liquid was removed by decantation. Further, this polymer was redissolved in 400 g of tetrahydrofuran, and then this solution was added to 5,000 g of methanol to reprecipitate the polymer in a slurry state. This slurry was filtered and vacuum-dried to obtain 44 g of the desired product as a white powder. The weight average molecular weight Mw measured by gel permeation chromatography in terms of polystyrene was 43,200, and the degree of dispersion Mw / Mn was 2.9. The elemental analysis was 50.8% carbon, 7.6% hydrogen, 5.1% nitrogen, and 25.6% sulfur. From the thermogravimetric analysis, the 5% weight loss temperature was 186 ° C. The obtained HPEMA has a structure represented by the formula (6) (refractive index at a wavelength of 589 nm (NaD line): 1.611).

<Two-photon lithography>.
The two-photon lithography used the optical apparatus shown in FIG. This optical device irradiates a near-infrared femtosecond laser (wavelength 700 to 800 nm, frequency 80 MHz, pulse width less than 100 femtoseconds) from the light source 1 toward the mirror 2 in the direction of arrow A. In two-photon lithography, two photons having a wavelength of 700 to 800 nm are absorbed simultaneously in the two-photon absorption process, so that absorption in the ultraviolet region of 350 to 400 nm, which is a half wavelength, can be excited. The laser irradiated on the mirror 2 passes through the pin 3 after passing through the lens 3. Subsequently, the laser passes through the lens 5 and is split by the mirror 6. A part of the divided laser beam is irradiated toward the objective lens 7 (magnification 100 times, numerical aperture NA = 0.9). The objective lens 7 adjusts the condensing point of the laser by moving up and down in the direction of arrow B in the figure. The laser whose focusing point is adjusted is irradiated onto the substrate 9 on which the sample 8 is applied. Since the substrate 9 is disposed on the xyz stage 10 and can move with high precision in the x, y, and z directions by adopting a PC control stepping motor, the sample 8 is three-dimensionally irradiated. The curing reaction can be advanced. A lens 11 and a CCD camera 12 are arranged on the opposite side of the substrate 9 via the mirror 6, and the objective lens 7 and the substrate 9 can be moved while observing the state of the curing reaction on the sample 8. it can.

[Example 1: Preparation of HPS-containing two-photon absorption polymerizable composition and stereolithography (spacer film formation)]
(A) 4.4 mg of trimethylolpropane triacrylate (hereinafter abbreviated as TPT) as the polymerizable compound, (b) 22.0 mg of HPS synthesized in Reference Example 2 as the dithiocarbamate group-containing polymer compound, and (c) 2 As a photon absorbing compound, 0.2 mg of 4,4′-bis (diethylamino) benzophenone (ethyl Michler's ketone, hereinafter abbreviated as EMK) is mixed, and the weight ratio (a) / (b) / (c) of each component is A two-photon absorption polymerizable composition of 20/100/1 was obtained.
Next, 22.0 mg of γ-butyrolactone having the same weight as the dithiocarbamate group-containing polymer compound (b) was added as a solvent to the obtained composition and dissolved to prepare a varnish.

  As shown in FIG. 2, two 7.5 μm-thick polyimide films processed to about 3 mm × 5 mm as spacers are placed on a pre-cleaned glass slide with the long sides facing each other at intervals of about 5 mm. A cover glass of about 10 mm × 5 mm was arranged on the top. Next, the varnish was injected into the gap by capillary action by dropping the varnish through a 0.45 μm filter into the opening of the gap between the slide glass and the cover glass, thereby preparing a test cell.

This test cell was irradiated with a laser so that the irradiation intensity in the immediate vicinity of the objective lens 7 would be 8 mW at a wavelength of 740 nm, a frequency of 80 MHz, and a pulse width of 100 femtoseconds using the optical device, and the optical modeling of a fine three-dimensional structure. Tried.
After laser irradiation, the unreacted composition was washed with γ-butyrolactone, and the cover glass was removed. When the obtained photocured material having a fine three-dimensional structure was observed with an optical microscope, it was confirmed that a desired fine three-dimensional structure was formed.

The formed pattern is schematically shown in FIG. More specifically, stripes having a line width of about 350 nm are formed at intervals of 2 μm between 100 μm in the horizontal direction in FIG. 3 as the first layer, and stripes having a line width of about 350 nm between the depths of 200 μm in FIG. Are formed on the stripes, and stripes having a line width of about 350 nm are formed at intervals of 2 μm so that the phase is shifted by 1 μm from the first layer as the third layer, and the second layer is formed as the fourth layer on the top. A fine three-dimensional structure in which the same stripe as the layer was arranged was formed.
The optical microscope image of the observed photocured product is shown in FIG.

[Examples 2 to 24]
In Example 1, it carried out similarly to Example 1 except having changed the weight ratio and spacer thickness of (a), (b), (c) into the value shown in Table 1. The results are shown in Table 1. In any example, a desired fine three-dimensional structure was formed.

[Comparative Examples 1-2]
In Example 1, it carried out similarly to Example 1 except having changed the weight ratio and spacer thickness of (a), (b), (c) into the value shown in Table 1. The results are shown in Table 1. In any of the examples, photocuring did not occur and a desired fine three-dimensional structure could not be formed.

[Example 25: Preparation of HPS-containing two-photon absorption polymerizable composition and stereolithography (spin coating film formation)]
(A) 39.0 mg of TPT as a polymerizable compound, (b) 19.5 mg of HPS synthesized in Reference Example 2 as a polymer compound containing a dithiocarbamate group, and (c) 0.6 mg of EMK as a two-photon absorption compound were mixed. A two-photon absorption polymerizable composition having a weight ratio (a) / (b) / (c) of each component of 200/100/3 was obtained.
Next, 19.5 mg of toluene having the same weight as that of the polymer compound containing (b) dithiocarbamate group was added as a solvent to the obtained composition and dissolved to prepare a varnish.

The varnish that passed through a 0.45 μm filter was spin-coated on a glass substrate previously washed at 2,000 rpm for 30 seconds to form a thin film. This thin film was used as it was as a test cell without being dried by heating.
This test cell was irradiated with a laser in the same manner as in Example 1 to attempt optical modeling of a fine three-dimensional structure.
After laser irradiation, the unreacted composition was washed with toluene, and the obtained photocured product having a fine three-dimensional structure was observed with an optical microscope. As a result, it was confirmed that a desired fine three-dimensional structure was formed.

[Examples 26 to 31]
In Example 25, it carried out like Example 25 except having changed the weight ratio of (a), (b), (c) into the value shown in Table 2. The results are shown in Table 2. In any example, a desired fine three-dimensional structure was formed.

[Comparative Example 3]
In Example 25, it carried out like Example 25 except having changed the weight ratio of (a), (b), (c) into the value shown in Table 2. The results are shown in Table 2. As in Comparative Examples 1 and 2, photocuring did not occur and the desired fine three-dimensional structure could not be formed.

[Example 32: Preparation and stereolithography (spacer film formation) of HPEMA-containing two-photon absorption polymerizable composition]
(A) 132.9 mg of TPT as a polymerizable compound, (b) 332.2 mg of HPEMA synthesized in Reference Example 4 as a polymer compound containing a dithiocarbamate group, and (c) 6.6 mg of EMK as a two-photon absorption compound were mixed. A two-photon absorption polymerizable composition in which the weight ratio (a) / (b) / (c) of each component was 40/100/2 was obtained.
Next, 332.2 mg of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) having the same weight as the (b) dithiocarbamate group-containing polymer compound was added as a solvent to the resulting composition and dissolved to prepare a varnish.

Using the prepared varnish, a test cell was prepared in the same manner as in Example 1 except that the spacer thickness was 25 μm, and then laser irradiation was performed in the same manner as in Example 1 to attempt optical modeling of a fine three-dimensional structure.
After laser irradiation, the unreacted composition was washed with PGMEA, and the cover glass was removed. When the obtained photocured material having a fine three-dimensional structure was observed with an optical microscope, it was confirmed that a desired fine three-dimensional structure was formed. An optical microscope image is shown in FIG.

[Examples 33 to 41]
In Example 32, it carried out like Example 32 except having changed the weight ratio and spacer thickness of (a), (b), (c) into the value shown in Table 3. The results are shown in Table 3. In any example, a desired fine three-dimensional structure was formed.

[Comparative Examples 4 to 5]
In Example 32, it carried out like Example 32 except having changed the weight ratio and spacer thickness of (a), (b), (c) into the value shown in Table 3. The results are shown in Table 3. In any of the examples, photocuring did not occur and a desired fine three-dimensional structure could not be formed.

[Example 42: Preparation of HPEMA-containing two-photon absorption polymerizable composition and stereolithography (spin coat film)]
(A) 35.0 mg of TPT as a polymerizable compound, (b) 17.5 mg of HPEMA synthesized in Reference Example 4 as a polymer compound containing a dithiocarbamate group, and (c) 0.5 mg of EMK as a two-photon absorption compound were mixed. A two-photon absorption polymerizable composition having a weight ratio (a) / (b) / (c) of each component of 200/100/3 was obtained.
Next, 17.5 mg of toluene having the same weight as (b) the dithiocarbamate group-containing polymer compound was added as a solvent to the obtained composition and dissolved to prepare a varnish.

Using the prepared varnish, a test cell was prepared in the same manner as in Example 25, and then laser irradiation was performed in the same manner as in Example 1 to attempt optical modeling of a fine three-dimensional structure.
After laser irradiation, the unreacted composition was washed with toluene, and the obtained photocured product having a fine three-dimensional structure was observed with an optical microscope. As a result, it was confirmed that a desired fine three-dimensional structure was formed.

[Examples 43 to 45]
In Example 42, it carried out similarly to Example 42 except having changed the weight ratio of (a), (b), (c) into the value shown in Table 4. The results are shown in Table 4. In any example, a desired fine three-dimensional structure was formed.

[Comparative Example 6]
In Example 42, it carried out similarly to Example 42 except having changed the weight ratio of (a), (b), (c) into the value shown in Table 4. The results are shown in Table 4. As in Comparative Examples 4 to 5, photocuring did not occur and a desired fine three-dimensional structure could not be formed.

[Example 46: Evaluation of refractive index]
(A) 500 mg of TPT as a polymerizable compound, (b) 1,000 mg of HPS synthesized in Reference Example 2 as a polymer compound containing a dithiocarbamate group, and (c) 10 mg of EMK as a two-photon absorption compound were mixed. Weight ratio (a) / (b) / (c) is 50/1
A two-photon absorption polymerizable composition of 00/1 was obtained.
Next, 3.54 g of cyclohexanone was added as a solvent to the obtained composition and dissolved to prepare a varnish. After spin coating on a silicon substrate at 300 rpm × 5 seconds and 2,500 rpm × 30 seconds, 5 ° C. at 5 ° C. The film was dried at 80 ° C. for 10 minutes for 10 minutes to form a thin film.
About the obtained thin film, the film thickness and the refractive index were measured using the incident angle spectroscopic ellipsometer (JA Woollam company make, M-2000VI). The results are shown in Table 5.

[Examples 47 to 48]
In Example 46, it carried out like Example 46 except having changed the weight ratio of (a), (b), (c) into the value shown in Table 5. The results are shown in Table 5.

[Examples 49 to 51]
In Example 46, the weight ratio of (a), (b), (c) was changed to the values shown in Table 5, and the thin film formed in addition was cured by UV irradiation for 20 minutes. The same was done. The results are shown in Table 5.

[Comparative Example 7: Evaluation of refractive index]
TPT 10.0 mg, Nano Society Society 6th Conference Proceedings Collection (May 2008), hyperbranched polymer 100.0 mg described in p173, and EMK 0.1 mg were mixed.
About the obtained composition, when the refractive index was measured using Abbe refractometer 2T (product made from Atago Co., Ltd.), the refractive index in wavelength 589nm (NaD line | wire) was 1.476. The results are shown in Table 5.

  The two-photon absorption polymerizable composition according to the present invention can be effectively used for fine optical devices such as polymer optical waveguides, polymer optical fibers, optical display materials, diffraction gratings, photonic crystals, and microreactors.

FIG. 1 is a schematic diagram illustrating an optical device used in the examples. FIG. 2 is a schematic diagram showing a procedure for producing the test cell used in Example 1. FIG. 3 is a schematic diagram showing a pattern of a fine three-dimensional structure produced in Example 1. FIG. 4 is an optical microscope image of a fine three-dimensional structure produced in Example 1. FIG. 5 is an optical microscope image of a fine three-dimensional structure produced in Example 32.

Claims (10)

A two-photon absorption polymerizable composition comprising (a) a polymerizable compound, (b) a dithiocarbamate group-containing polymer compound, and (c) a two-photon absorption compound. The two-photon absorption polymerizable composition according to claim 1, wherein the weight average molecular weight of the (b) dithiocarbamate group-containing polymer compound measured by gel permeation chromatography in terms of polystyrene is 500 to 200,000. The two-photon absorption polymerizable composition according to claim 1 or 2, wherein the (b) dithiocarbamate group-containing polymer compound is a branched polymer. The two-photon absorption polymerizable composition according to claim 3, wherein the (b) dithiocarbamate group-containing polymer is a branched polymer represented by the formula (1).
(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or a carbon atom. Represents an arylalkyl group of formula 7 to 12, or R ² and R ³ may be bonded to each other to form a ring with a nitrogen atom, A ¹ represents formula (2) or formula (3), n is the number of repeating unit structures and represents an integer of 2 to 100,000.)
(In the formula, A ² has 1 to 3 carbon atoms which may contain an ether bond or an ester bond.
0 represents a linear, branched or cyclic alkylene group, and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms. 1 to 20 alkoxy groups, nitro groups, hydroxyl groups, amino groups, carboxyl groups or cyano groups are represented. ) The two-photon absorption polymerizable composition according to any one of claims 1 to 4, wherein the polymerizable compound (a) is a polymerizable compound having an ethylenically unsaturated bond. The two-photon absorption polymerizable composition according to any one of claims 1 to 4, wherein the polymerizable compound (a) is a polymerizable compound having a cationic polymerizable moiety. A varnish containing the two-photon absorption polymerizable composition according to any one of claims 1 to 6. A thin film produced from the varnish according to claim 7. The two-photon absorption polymerizable composition according to any one of claims 1 to 6, wherein (c) the two-photon absorption compound contained therein has a longer wavelength than the linear absorption band of the two-photon absorption compound, and linear absorption. A photocuring method comprising polymerizing the two-photon absorption polymerizable composition by utilizing multiphoton absorption of two or more photons induced by irradiation with a laser beam having a wavelength that does not exist. An optical device structure obtained by curing the two-photon absorption polymerizable composition according to any one of claims 1 to 6 by two-photon absorption polymerization.