JP2721572B2 - Photosensitive resin composition, pattern using the same, and pattern manufacturing method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photosensitive resin composition which gives a pattern having a large difference in refractive index and a difference in unevenness, a pattern using the same, and a method for producing a pattern.

[Prior art] Conventionally, a cross-linking reaction or a molecule disintegration reaction occurs in an exposed portion of a photosensitive resin, and the exposed portion becomes hardly soluble or easily solubilized. A relief pattern was prepared by a method of removing the photosensitive resin [Conventional method (1)].

In addition, a thin film is formed from a photosensitive resin composition obtained by doping a resin with a relatively volatile photoreactive substance having a higher refractive index than the resin, and then the thin film is irradiated with ultraviolet light, and the exposed portion is doped. A method of forming a pattern having a refractive index difference between an exposed portion and a non-exposed portion by rocking a substance and evaporating and removing a doping material in a non-exposed portion, that is, a so-called photo-rocking method (conventional method (2)). Known [Applied Physics Lett
ers), Vol. 26, No. 6, pp. 303-306 (1975)]. According to this method, it is reported that the film thickness of the exposed part is increased by about 10% as compared with the unexposed part.

Further, a thin film is formed from a photosensitive resin composition comprising an acrylic acid or methacrylic acid ester-based polymer or copolymer having a photoreactive double bond at the alcohol residue of the ester and an aromatic ketone or aromatic aldehyde. And
Then, the thin film is irradiated with ultraviolet rays, and then the unreacted aromatic ketone or aromatic aldehyde is removed to form a pattern having both a refractive index difference and an unevenness difference between an exposed portion and a non-exposed portion. [Conventional method (3)] is known (see JP-A-62-95525 and JP-A-62-95526).

[Problem to be Solved by the Invention] In the relief pattern of the photosensitive resin produced by the conventional method (1), the difference in the refractive index between the exposed portion and the non-exposed portion is very little or very small. In the pattern produced by the conventional method (2), the difference in the refractive index between the exposed portion and the non-exposed portion and the change in the thickness of the uneven portion are not sufficient.

According to the conventional method (3), the exposed portion of the photosensitive resin composition has a higher refractive index than the non-exposed portion, and a clear pattern having a large thickness can be produced. And heat resistance is not always sufficient.

One object of the present invention is to provide a photosensitive composition having a surface relief structure in which exposed portions have a higher refractive index than non-exposed portions and have a large thickness, and provide a pattern having high organic solvent resistance and heat resistance and high shape stability. An object of the present invention is to provide a conductive resin composition.
Another object of the present invention is to provide a method for producing the above pattern using the photosensitive resin composition.
Another object of the present invention is to provide a pattern formed from the photosensitive resin composition.

[Means for Solving the Problems] According to the present invention, one of the above objects is to provide a structural unit represented by the following general formula (I) (hereinafter referred to as a structural unit (I)) from 1 to 97. Mol%, 1 to 97 mol% of a structural unit represented by the following general formula (II) (hereinafter referred to as a structural unit (II)), and a structural unit represented by the following general formula (III) (hereinafter referred to as Structural unit (III))
An aggregate (A) having 1 to 97 mol% and 1 to 97 mol% of a structural unit represented by the following general formula (IV) (hereinafter referred to as a structural unit (IV)); This is achieved by providing a photosensitive resin composition comprising a compound (B) selected from the group consisting of aromatic aldehydes and aromatic ketones.

Structural unit (I): [In the formula, X ¹ represents a hydrogen atom or an alkyl group, and Y ¹ represents a cycloalkenyl group or a general formula shown below. Represents a group represented by Here, Z ¹ represents a divalent hydrocarbon group, and R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group or an alkenyl group. ] Structural unit (II): [Wherein, X ² represents a hydrogen atom or an alkyl group, and Z ² represents 2
R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or an alkyl group. ] Structural unit (III): [Wherein X ³ represents a hydrogen atom or an alkyl group, Y ² represents a phenyl group, an alkoxycarbonyl group or a carbamoyl group, and the hydrogen atom in the general formula (III) may be substituted by a fluorine atom. Good. ] Structural unit (IV): [Wherein X ⁴ represents a methylene group or an oxygen atom, X ⁵ ,
X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ each represent a hydrogen atom or an alkyl group, and n is an integer of 0 to 3. The polymer (A) constituting the photosensitive resin composition used in the present invention contains 5-90 mol% of the structural unit (I), 2-80 mol% of the structural unit (II), and IV) to 2
Preferably, the content of the structural unit (I) is 10 to 80 mol%.
60 mol%, 10 to 60 mol% of the structural unit (II), and the ratio of the structural unit (II) to the structural unit (IV) is 5: 2 to 5: 6.
(Molar ratio) is more preferable.

X ¹ in the above structural units (I), X ² in the structural unit ^{(II), X 5, X} 6, X 7, X 8, X 9 and in X ³ and structural units in the structural unit (III) (IV) The alkyl group represented by X ¹⁰ is preferably a lower alkyl group having 4 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Further, R ¹ , R ² and R ³ in the structural unit (I) and in the structural unit (II)
The alkyl group represented by R ⁴ , R ⁵ and R ⁶ may have a branched chain or any substituent, and may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an amyl group, a hexyl group, A lower alkyl group having 8 or less carbon atoms, such as a heptyl group and an octyl group, is preferred. The alkenyl group represented by each of R ¹ , R ² and R ³ is a 2-butenyl group,
3-methyl-2-butenyl group, 3-pentenyl group, 4-
A methyl-3-pentenyl group is preferred. Structural unit (I)
Is preferably an alkylene group having 2 to 8 carbon atoms which may have a branched chain, as the divalent hydrocarbon group represented by Z ^{1 in} formula (I) and Z ² in the structural unit (II). Preferred examples of Y ¹ in the structural unit (I) include an allyl group, a 2-butenyl group, a 3-butenyl group, a 2-methyl-2-propenyl group, a 2-heptenyl group, a 3-heptenyl group, a 4-heptenyl group, 2-methyl-2-butenyl group, 3-methyl-2
-Butenyl group, 2-ethyl-2-propenyl group, 2-methyl-3-butenyl group, 1,2-dimethyl-2-propenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5- Hexenyl group, 1,1-dimethyl-2-butenyl group, 1,2-dimethyl-2-butenyl group, 1,3-dimethyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, 3-methyl -2-heptenyl group, 2-methyl-2-
Heptenyl group, 2-methyl-2-cyclohexenyl group,
3-methyl-2-cyclohexenyl group, geranyl group, isogeranyl group, neryl group, lavanjuyl group, 6-methylgeranyl group, 1-methylgeranyl group, 6-ethylgeranyl group, perillyl group, huanesyl group, geranylgeranyl group, β -Cyclogeranylgeranyl group and the like.

The group in the structural unit (II) [Hereinafter referred to as group Y ^3] as the 2,3-epoxypropyl group, 2,3-epoxy butyl group, 3,4-epoxy butyl group, 2,3-epoxy-2-
Methylpropyl group, 2-methyl-2,3-epoxybutyl group, 3-methyl-2,3-epoxybutyl group, 2,3-epoxyheptyl group, 5,6-epoxyheptyl group, 3-methyl-2, Examples thereof include a 3-epoxybutyl group, a 4-methyl-2,3-epoxyheptyl group, and a 4-methyl-5,6-epoxyheptyl group.

Preferred examples of the alkoxycarbonyl group represented by Y ² in the structural unit (III) include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentaoxycarbonyl group, a hexanoxycarbonyl group, and a heptanoxy group Examples include a carbonyl group and a cyclohexoxycarbonyl group.

X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X in structural unit (IV)
¹⁰ is preferably a hydrogen atom. Further, n in the structural unit (IV) is preferably 0 or 1.

The polymer (A) is obtained by copolymerizing acrylic acid or an ester thereof which may be substituted at the α-position with an alkyl group and a comonomer forming the structural unit (IV), or copolymerizing the acrylic acid or an ester thereof with the structural unit ( by copolymerization of the comonomers forming the comonomer structural units (IV) to form the III) to obtain a polymer, then the reaction mixture with an alcohol having an alcohol having a polymer and a group Y ^1, and the group Y ³ Or copolymerization of an acrylic acid derivative forming the structural unit (I) with an acrylic acid derivative forming the structural unit (II) and a comonomer forming the structural unit (IV), or these acrylic acid derivatives and the structural unit (III)
Can be produced by copolymerization with a comonomer that forms

The acrylic acid derivative forming the structural unit (I) includes allyl methacrylate, allyl acrylate,
(Or 3) -butenyl methacrylate, 2 (or 3) -butenyl acrylate, 2-methyl-2-propenyl methacrylate, 2-methyl-2-propenyl acrylate, 2 (or 3 or 4) -heptenyl methacrylate, 2 (Or 3 or 4) -heptenyl acrylate, 2-methyl-2- (or 3) -butenyl methacrylate, 2-methyl-2 (or 3) -butenyl acrylate, 2-ethyl-2-propenyl methacrylate, 2 -Ethyl-2-propenyl acrylate, 1,2-
Dimethyl-2-propenyl methacrylate, 1,2-dimethyl-2-propenyl acrylate, 2 (or 3 or 4 or 5) -hexenyl methacrylate, 2 (or 3 or 4 or 5) -hexenyl acrylate,
1 (or 1,2 or 1,3 or 2,3) -dimethyl-2-butenyl methacrylate, 1,1 (or 1,2 or 1,3 or 2,3) -dimethyl-2-butenyl acrylate, 2
(Or 3) -methyl-2-heptenyl methacrylate, 2 (or 3) -methyl-2-heptenyl acrylate or other acrylic acid derivative in which an alcohol residue is in a chain; 2 (or 3) -methyl- Acrylic acid derivatives in which alcohol residues such as 2-cyclohexenyl methacrylate, 2 (or 3) -methyl-2-cyclohexenyl acrylate are cyclic; geranyl methacrylate, geranyl acrylate, neryl methacrylate, neryl acrylate, isogeneryl methacrylate, Isogeranyl acrylate, lavanjuyl methacrylate, lavanjuyl acrylate, 6-methylgeranyl methacrylate, 6-methylgeranyl acrylate, 1
-Methylgeranyl methacrylate, 1-methylgeranyl acrylate, 6-ethylgeranyl methacrylate, 6
Esters of a chain or cyclic terpene alcohol having two non-conjugated double bonds such as ethylgeranyl acrylate, perillyl methacrylate, perillyl acrylate, etc. with acrylic acid or methacrylic acid; phenyl methacrylate, phenyl acrylate, Geranylgeranyl methacrylate, geranylgeranyl acrylate, β
A non-conjugated double bond such as cyclogeranylgeranyl methacrylate, β-cyclogeranylgeranyl acrylate;
An ester of a linear or cyclic terpene-based alcohol having at least one acrylic acid or methacrylic acid is exemplified. Among these, allyl methacrylate, 2-methyl-2-propenyl methacrylate, 2-butenyl methacrylate, 2-methyl-2-butenyl methacrylate,
2-hexenyl methacrylate, 3-hexenyl methacrylate, and geranyl methacrylate are preferred from the viewpoint of easy availability of alcohol as a raw material and ease of ester synthesis.

The acrylic acid derivatives forming the structural unit (II) include 2,3-epoxypropyl methacrylate, 2,3-epoxypropyl acrylate, 2,3-epoxybutyl methacrylate, 2,3-epoxybutyl acrylate, 3,4
-Epoxybutyl methacrylate, 3,4-epoxybutyl acrylate, 2-methyl-2,3-epoxypropyl methacrylate, 2-methyl-2,3-epoxypropyl acrylate, 2,3-epoxyheptyl methacrylate, 5,6-epoxy Heptyl methacrylate, 2,3-epoxyheptyl acrylate, 5,6-epoxyheptyl acrylate, 2 (or 3) -methyl-2,3-epoxybutyl methacrylate, 2 (or 3) -methyl-2,3
-Epoxybutyl acrylate, 4-methyl-2,3-epoxyheptyl methacrylate, 4-methyl-5,6-epoxyheptyl acrylate. Among these, 2,3-epoxypropyl methacrylate, 2,3-epoxybutyl methacrylate, and 3,4-epoxybutyl methacrylate are preferred from the viewpoint of ease of ester synthesis.

Comonomers forming the structural unit (III) include methacrylic acid; methyl methacrylate, ethyl methacrylate,
Alkyl methacrylates such as propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, amyl methacrylate, and cyclohexyl methacrylate; acrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acryl Alkyl acrylates such as pentyl acid, hexyl acrylate, amyl acrylate, and cyclohexyl acrylate; and substituted styrenes such as methacrylamide, acrylamide, styrene, and α-methylstyrene. A hydrogen atom in the structural unit (III) may be replaced by a fluorine atom.

Examples of the comonomer forming the structural unit (IV) include maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 7-oxa-5-norbornene-2,3-dicarboxylic anhydride, and 7-oxa-5. -Methyl-5-norbornene-2,3-dicarboxylic anhydride, 7-oxa-5-ethyl-5-norbornene-2,3-dicarboxylic anhydride, 4-
Methyl-7-oxa-5-norbornene-2,3-dicarboxylic anhydride, 1,4-dimethyl-7-oxa-5-norbornene-2,3-dicarboxylic anhydride, 4-ethyl-7
-Oxa-5-norbornene-2,3-dicarboxylic anhydride, 1,2,3,4,4a, 5,8,8a-octahydro-1,4: 5,8-dioxanaphthalene-2,3- Dicarboxylic anhydride, 1,2,3,4,4
Acids such as a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dicarboxylic anhydride, 3-methyl-5-norbornene-2,3-dicarboxylic anhydride Anhydrides can be mentioned. Among these, maleic anhydride, 5
-Norbornene-2,3-dicarboxylic anhydride and 7-oxa-5-norbornene-2,3-dicarboxylic acid are preferred from the viewpoint of easy synthesis.

The polymer (A) had a number average molecular weight in terms of polystyrene of 1,00, as determined by gel permeation chromatography.
Those in the range of 0 to 2,000,000 are preferred. More preferably, the polymer (A) has a number average molecular weight in the range of 100,000 to 1,500,000.

Examples of the compound (B) include, for example, benzaldehyde, benzophenone or a derivative thereof which may have a substituent. Specifically, the compound represented by the following general formula (V), general formula (VI) or general formula (VII) Is shown.

[In the formula, X ¹¹ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ , X ₁₆ , X ₁₇ , X ₁₈ and X ₁₉ each represent a hydrogen atom, an alkyl group or an alkoxy group having 7 or less carbon atoms, or a halogen atom. Represents X
_{^{20, X 21, X 22,}} X 23, X 24 and X ₂₅ each represent a hydrogen atom or a halogen atom. m is 0, 1 or 2. Preferred compounds (B) include benzophenone; 3 (or 4) -methylbenzophenone, 3 (or 4) -methoxybenzophenone, 3,3 ′ (or 4,4 ′)-dimethylbenzophenone, Substituted benzophenones such as 3,3 '(or 4,4')-dimethoxybenzophenone, 2,3 (or 2,4) -chlorobenzophenone, 3,4,5-trimethoxybenzophenone; 3-benzoyl Benzophenone; 3 (or 4) -methylbenzoyl-3 '(or 4')-methylbenzophenone; 3 (or 4) -methoxybenzoyl-3 '(or 4')-methoxybenzophenone, 3,
Meta-substituted benzophenones such as 3'-dibenzoylbenzophenone and 1,3,5-tribenzoylbenzene, benzaldehyde; 3 (or 4) -methylbenzaldehyde, 3 (or 4) -methoxybenzaldehyde, 3,4
-Substituted benzaldehydes such as -dimethylbenzaldehyde and 3,4-dimethoxybenzaldehyde. Of these, benzaldehyde, benzophenone, 3-benzoylbenzophenone, 3,3'-dibenzoylbenzophenone and 1,3,5-tribenzoylbenzene are preferred because of their ease of synthesis, and 3-benzoylbenzophene is preferred. Non- and 1,3,5-tribenzoylbenzene have good photoreactivity and can increase the unevenness difference and the refractive index difference between exposed and unexposed parts, and the resulting pattern has a high resistance. It is particularly preferable because it has high organic solvent properties and high heat resistance.

It is preferable to add a tertiary amine such as benzyldimethylamine to the polymer (A) in that the thermal reactivity can be increased.

The composition ratio of the polymer (A) and the compound (B) is 10: 1 to 1:
A range of 10 (weight ratio) is preferable, and a range of 2: 1 to 1: 2 (weight ratio) is more preferable. The ratio of the structural unit (I) and the compound (B) in the polymer (A) is 10: 1 to 1:20 (molar ratio).
Is preferable, and the range of 5: 1 to 1:10 (molar ratio) is more preferable.

According to the present invention, another object is to provide a pattern using the above-mentioned photosensitive resin composition, comprising the following steps (a), (b) and (c): This is achieved by providing a fabrication method.

(A) a step of forming a thin film of the photosensitive resin composition.

(B) A step of partially irradiating the thin film with ultraviolet rays according to a desired pattern.

(C) a step of removing the unreacted compound (B) from the thin film.

In the step (a), the polymer (A) and the compound (B) are dissolved in a solvent that dissolves them, and the resulting solution is used to form a thin film by a casting method, a bar coating method, a spin coating method, or the like. To form If necessary, the solvent is removed from the thin film by subjecting the thin film to a vacuum treatment or a heat treatment.
The method of forming the thin film is selected according to the desired thickness or form of the thin film. The thickness of the thin film is preferably in the range of 0.1 to 20 μm. Generally, when the thickness is large, a casting method is used, and when the thickness is small, a bar coating method or a spin coating method is used.

In the step (b) following the step (a), the thin film is partially irradiated with ultraviolet rays having a wavelength of 200 to 450 nm according to a desired pattern. This causes a photoreaction between the structural unit (I) and the compound (B). The light source high-pressure mercury lamp, N ₂ gas lasers, such as He-Cd laser is used. As a method of forming a desired pattern, a mask exposure method using a photomask, a two-beam interference exposure method, a laser beam direct writing method, or the like is employed.

The removal of the unreacted compound (B) in the step (c) following the step (b) is performed by heat-treating the thin film under reduced pressure at a temperature in the range of 20 to 120 ° C for 15 to 30 hours (hereinafter, referred to as pre-heat treatment). ) And then heat-treating under normal pressure at a temperature in the range of 105 to 230 ° C for 15 minutes to 40 hours (hereinafter referred to as post-heat treatment) or pre-heat-treating and then a thin film of the photosensitive resin composition entire strength of in the range of 10~40mW / cm ^2,
UV light having a wavelength in the range of 200 to 450 nm for 30 seconds to 10
It is preferable to carry out by irradiating for minutes. Thereby, a pattern having a desired difference in refractive index and a difference in unevenness is obtained. Since the structural units (I), (II) and (IV) contained in the pattern are thermally crosslinked, the pattern has high organic solvent resistance and heat resistance. The above post heat treatment is performed at a temperature in the range of 150 to 200 ° C for 1 to 5
More preferably, it is carried out for a period of time or at a temperature in the range of 110 to 140 ° C. for 10 to 25 hours. Further, it is preferable to irradiate ultraviolet rays for the post-heat treatment after the above-mentioned pre-heat treatment, since a pattern having more resistance to organic solvent and heat can be obtained. When the above pre-heat treatment is performed at a temperature in the range of 100 to 120 ° C. for 15 to 30 hours, a pattern having high organic solvent resistance and heat resistance can be obtained even if the post heat treatment is omitted.

From the photosensitive resin composition by the above method, an optical waveguide,
A pattern such as a diffraction grating, a grating lens, a Fresnel lens, and a hologram lens can be manufactured. Further, by doping a photosensitive resin composition with various nonlinear optical materials, an optical waveguide having a nonlinear effect can be manufactured. These patterns are extremely excellent in optical transparency, organic solvent resistance and heat resistance.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples.

Example 1 2-butenyl methacrylate 70 after N ₂ substitution in a reaction vessel
g, 10 g of methyl methacrylate, 71 g of 2,3-epoxypropyl methacrylate, 98 g of maleic anhydride, 600 mg of azobisisobutyronitrile, and 900 ml of dioxane, sealed and heated in a 53 ° C water bath for 24 hours for polymerization reaction. Went. The obtained reaction solution was poured into 4 l of methanol, and the product was precipitated and dried to obtain polymer (A).
0 g was obtained. This polymer (A) shows 2
-Butenyl methacrylate vs. methyl methacrylate vs. 2,
It was confirmed that the molar ratio of 3-epoxypropyl methacrylate to maleic anhydride was 1: 2: 1: 1. The polymer (A) had a number average molecular weight in terms of polystyrene of 250,000 as determined by gel permeation chromatography. The above polymer (A) 10
And a composition consisting of 6 parts of 3-benzoylbenzophenone in toluene, and using the resulting solution on a glass substrate by spin coating to form a thin film (thickness: 1.5 μm).
Was formed. A 25 mW / cm ² ultraviolet ray is applied to this thin film through a photomask having a line and space with a period of 35 μm.
Irradiated for 120 seconds. After the irradiation, the photomask was removed, and a pre-heat treatment was performed in a vacuum dryer at 100 ° C. and 0.2 mmHg for 20 hours. Thereafter, the entire surface of the thin film is irradiated with ultraviolet rays of 40 mW / cm ² for 7 minutes, and further subjected to a heat treatment at 120 ° C. and normal pressure for 2 hours to remove the unreacted compound (B). ,
A diffraction grating pattern having a refractive index difference and a concavo-convex difference was produced.

The diffraction efficiency of this diffraction grating is 3 for light with a wavelength of 633 nm.
3%. The diffraction grating was left in a saturated vapor of methyl methacrylate at 50 ° C. for 100 hours, but its diffraction efficiency did not change. From this, it was determined that the shape and the refractive index of the diffraction grating did not change.

The diffraction grating was heated at 160 ° C. (normal pressure) for 8 hours, but the diffraction efficiency did not change.

Examples 2 to 9 In the same manner as in Example 1, a photosensitive resin composition comprising the polymer (A) and the compound (B) shown in Table 1 was prepared, and a photosensitive resin composition having the composition shown in Table 1 was prepared. A diffraction grating was produced using the conductive resin composition under the same conditions as in Example 1.

Example 1 Using the Diffraction Grating Produced in Each Example
When the same organic solvent resistance and heat resistance tests were performed as in the above, the diffraction efficiency did not change in any of the diffraction gratings.

 In Table 1, parts indicate parts by weight.

Example 10 10 parts of polymer (A) having the same composition as in Example 1 and 3
A composition comprising 6 parts of benzoylbenzophenone was dissolved in toluene, and a thin film (thickness: 1.5 μm) was formed on a glass substrate by spin coating using the obtained solution. The thin film was irradiated with ultraviolet rays of 25 mW / cm ² for 150 seconds through a photomask having a line and space with a period of 35 μm. After the irradiation, the photomask was removed, and heat treatment was performed in a vacuum dryer at 110 ° C. and 0.2 mmHg for 20 hours. Thereafter, the entire surface of the thin film is irradiated with ultraviolet rays of 25 mW / cm ² for 5 minutes to remove the unreacted compound (B), thereby producing a diffraction grating pattern having a difference in refractive index and a difference in unevenness. did.

The diffraction efficiency of this diffraction grating is 3 for light with a wavelength of 633 nm.
It was 0%, and the organic solvent resistance and the heat resistance were good as in the diffraction grating of Example 1.

Example 11 Geranyl methacrylate 39 g after N ₂ substitution in a reaction vessel,
26 g of 2,3-epoxypropyl methacrylate, 38 g of methyl methacrylate, 40 g of maleic anhydride, 135 mg of azobisisobutyronitrile and 450 ml of dioxane were charged, sealed and heated in a 55 ° C water bath for 24 hours to carry out a polymerization reaction. I got it. The obtained reaction solution was poured into 1.5 l of methanol, and the product was precipitated and dried to obtain the polymer (A).
60 g were obtained. From the results of NMR measurement, it was confirmed that this polymer (A) was a copolymer having a molar ratio of geranyl methacrylate to 2,3-epoxypropyl methacrylate to methyl methacrylate to maleic anhydride of 1: 1: 1: 2: 1. Was done. The number average molecular weight in terms of polystyrene of the polymer (A) determined by gel permeation chromatography was 300,000. A composition comprising 10 parts of the above polymer (A) and 8 parts of 1,3,5-tribenzoylbenzene is dissolved in toluene, and a thin film is formed on a glass substrate by spin coating using the resulting solution. (thickness
1.5 μm) and irradiated with ultraviolet light through a photomask under the same conditions as in Example 1. After that, the unreacted compound (B) is removed by pre-heat treatment, post-heat treatment and UV irradiation as in Example 1, and the pattern of the diffraction grating having the refractive index difference and the unevenness difference is changed. Produced.

This diffraction grating was excellent in organic solvent resistance and heat resistance similarly to the diffraction grating of Example 1.

COMPARATIVE EXAMPLE Using a photosensitive resin composition comprising 10 parts of a copolymer having a molar ratio of 2-butenyl methacrylate to methyl methacrylate of 1 to 3 and 6 parts of 3-benzoylbenzophenone, A diffraction grating was produced in the same manner.

The diffraction efficiency of this diffraction grating is 3 for light with a wavelength of 633 nm.
It was 0%. When the diffraction grating was heated at 150 ° C. (normal pressure) for 4 hours, the diffraction grating was deformed, and the diffraction efficiency was reduced to 25%.

[Effects of the Invention] According to the present invention, a pattern in which an exposed portion of a photosensitive resin has a higher refractive index than a non-exposed portion, has a surface relief structure having a large thickness, and is excellent in organic solvent resistance and heat resistance. Is obtained. Further, a method for producing the above-mentioned pattern using the photosensitive resin composition and a pattern produced using the photosensitive resin composition are obtained.

Claims (3)

(57) [Claims] 1. A compound represented by the following general formula (I) [In the formula, X ¹ represents a hydrogen atom or an alkyl group, and Y ¹ represents a cycloalkenyl group or a general formula shown below. Represents a group represented by Here, Z ¹ represents a divalent hydrocarbon group, and R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group or an alkenyl group. 1 to 97 mol% of the structural unit represented by the following general formula (II) [Wherein, X ² represents a hydrogen atom or an alkyl group, and Z ² represents 2
R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or an alkyl group. 1 to 97 mol% of the structural unit represented by the following general formula (III) [Wherein X ³ represents a hydrogen atom or an alkyl group, Y ² represents a phenyl group, an alkoxycarbonyl group or a carbamoyl group, and the hydrogen atom in the general formula (III) may be substituted by a fluorine atom. Good. And 0 to 97 mol% of the structural unit represented by the following general formula (IV): [Wherein X ⁴ represents a methylene group or an oxygen atom, X ⁵ ,
X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ each represent a hydrogen atom or an alkyl group, and n is an integer of 0 to 3. (A) having 1 to 97 mol% of a structural unit represented by the following formula:
And a compound (B) selected from the group consisting of an aromatic aldehyde and an aromatic ketone which may have a substituent. 2. A pattern produced by using the photosensitive resin composition according to claim 1. (A) the following general formula (I): [In the formula, X ¹ represents a hydrogen atom or an alkyl group, and Y ¹ represents a cycloalkenyl group or a general formula shown below. Represents a group represented by Here, Z ¹ represents a divalent hydrocarbon group, and R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group or an alkenyl group. 1 to 97 mol% of the structural unit represented by the following general formula (II) [Wherein, X ² represents a hydrogen atom or an alkyl group, and Z ² represents 2
R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or an alkyl group. 1 to 97 mol% of the structural unit represented by the following general formula (III) [Wherein X ³ represents a hydrogen atom or an alkyl group, Y ² represents a phenyl group, an alkoxycarbonyl group or a carbamoyl group, and the hydrogen atom in the general formula (III) may be substituted by a fluorine atom. Good. And 0 to 97 mol% of the structural unit represented by the following general formula (IV): [Wherein X ⁴ represents a methylene group or an oxygen atom, X ⁵ ,
X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ each represent a hydrogen atom or an alkyl group, and n is an integer of 0 to 3. (A) having 1 to 97 mol% of a structural unit represented by the following formula:
And forming a thin film of a photosensitive resin composition comprising a compound (B) selected from the group consisting of an aromatic aldehyde and an aromatic ketone which may have a substituent; (C) removing unreacted compound (B) from the thin film,
A pattern production method characterized by comprising: