JPH03251846A - Photosensitive resin composition, manufacture of pattern by using same, and this pattern - Google Patents

Abstract

PURPOSE:To enhance refractive index and dimensional stability and to form thick surface releaf structure by incorporating various specified polymers and an aromatic aldehyde or aromatic ketone compound in the composition. CONSTITUTION:The composition contains the polymer A having 1 - 97mol% structural units each represented by formula I, 1 - 97mol% structural units each represented by formula III, 0 - 97mol% structural units each represented by formula IV, and 1 - 97mol% structural units each represented by formula V, and the compound B selected from the aromatic aldehydes and the aromatic ketones. In formula I, X<1> is H or alkyl, Y<1> is cycloalkenyl or a group of formula II; in formulae III - V, each of X<2> and X<3> is H or alkyl; Z<2> is a divalent hydrocarbon group; each of R<4> - R<6> is H or alkyl; Y<2> is phenyl, alkoxycarbonyl or carbamoyl; X<4> is methylene or -O-; and each of X<5> - X<10> is H or alkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive resin composition that provides a pattern having a large difference in refractive index and a difference in unevenness, a pattern using the same, and a method for producing the pattern.

[Prior Art] Conventionally, a crosslinking reaction or a molecular collapse reaction occurs in the exposed areas of a photosensitive resin, and the exposed areas become poorly soluble or 5-solubilized. Method for removing photosensitive resin [Conventional method (1) was used to create a relief pattern.

In addition, a thin film is formed from a photosensitive resin composition obtained by doping a relatively volatile photoreactive substance having a higher refractive index than the resin, and then the thin film is irradiated with ultraviolet rays to dope the exposed areas. The so-called photolocking method [conventional method (2)] is a method of forming a pattern having a difference in refractive index between exposed and unexposed areas by locking a substance and evaporating the doped material in unexposed areas. [Applied Phys Letters]
sicsLetters), Volume 26, No. 6, No. 3
See pages 03-306 (1975). According to this method, it has been reported that the film thickness increases by approximately 10% in exposed areas compared to non-exposed areas.

Furthermore, a thin film is formed from a photosensitive resin composition consisting of an acrylic acid or methacrylic acid ester polymer or copolymer having a photoreactive double bond in the alcohol residue of the ester and an aromatic ketone or aromatic aldehyde. Then, the thin film is irradiated with ultraviolet rays, and the unreacted aromatic ketone or aromatic aldehyde is removed.
A method for producing a pattern that has both a refractive index difference and a unevenness difference between the original part and the unexposed part [Conventional method (3)] is known (
JP-A-62-95525 and JP-A-62955
(See Publication No. 26).

[Problems to be Solved by the Invention] In the relief pattern of photosensitive resin produced by the conventional method (1), there is almost no or extremely small difference in refractive index between exposed areas and non-exposed areas. In the pattern produced by the conventional method (2), the difference in refractive index between exposed and non-exposed areas and the change in thickness of uneven parts are not sufficient.

According to the conventional method (3), a clear pattern in which the exposed part of the photosensitive resin composition has a higher refractive index than the unexposed part and is thicker can be produced, but the organic solvent resistance of the obtained pattern is and heat resistance is not necessarily sufficient.

One object of the present invention is to provide a photosensitive pattern that has a surface relief structure with a higher refractive index and greater thickness than the exposed area or the unexposed area, has excellent solvent resistance and heat resistance, and has high shape stability. An object of the present invention is to provide a synthetic 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 produced using the photosensitive resin composition.

[Means for solving the problem] According to the present invention, one of the above objects is achieved by solving the following general formula (I
) (hereinafter referred to as structural unit (1)) from 1 to 97 mol%, a structural unit represented by the following general formula (n) (hereinafter referred to as structural unit (II))
1 to 97 mol% of the structural unit represented by the following general formula (DI) (hereinafter referred to as the structural unit (I [[))]
~97 mol%, and 1 structural unit represented by the following general formula (IV) (hereinafter referred to as structural unit (IV))
Provided is a photosensitive resin composition comprising a polymer (^) having ~97 mol% and a compound (B) selected from the group consisting of an aromatic aldehyde which may have a substituent and an aromatic ketone. This is achieved by

Structural unit (I): I [where xl represents a hydrogen atom or I represents an alkyl group, and Y
l represents a cycloalkenyl group or a group represented by the following general formula. Here, Zl represents a divalent hydrocarbon group, R',
R' and R3 each represent a hydrogen atom, an alkyl group or an alkenyl group. Co-structural unit (■): 1 In the U formula, X'' represents a hydrogen atom or an alkyl group, and Z!
represents a divalent hydrocarbon group, and R4, R5 and R@ each represent a hydrogen atom or an alkyl group. ] Structural unit (
■): 3 Y" [In the formula, x3 represents a hydrogen atom or an alkyl group, and Y'
represents a phenyl group, an alkoxycarbonyl group or a carbamoyl group, and the hydrogen atom in the general formula (I[[) may be substituted with a fluorine atom. ] Structural unit (■): S xl [In the formula, x4 represents a methylene group or an oxygen atom, and 1s
Sx*, x7, x"%x" and A) contains 5 to 90 mol% of structural unit (1) and contains 10
Contains ~60 mol%, and 10 to 60 mol% of structural unit (n)
It is more preferable that the ratio of the structural unit (I[) to the structural unit (IV) is in the range of 5=2 to 5:6 (molar ratio).

XI in the above structural unit (1), structural unit (II)
X′ in, x3 in the structural unit (I[[) and x6, xl, x7, X@, X in the structural unit (IV)
"The alkyl groups each represented by OYOHI and R3 and R4, R' and R1 in the structural unit (I[)
The alkyl groups each represented by may have a branched chain or an arbitrary substituent, and include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, amyl group, hexyl group,
A lower alkyl group having 8 or less carbon atoms such as a heptyl group or an octyl group is preferred. The alkenyl groups represented by R1, R1 and R3 above are 2-butenyl group, 3-methyl-2-butenyl group, 3-pentenyl group, 4-methyl-3
-Pentenyl group is preferred. Z in structural unit (I)
1 and 2 in the structural unit (If)! The divalent hydrocarbon groups represented by are preferably alkylene groups having 2 to 8 carbon atoms which may have a branched chain. structural unit (r)
Preferable examples of Yl in are allyl group, 2-butenyl group, 3-butenyl group, 2-methyl-2-propenyl group, 2-hebutenyl group, 3-hebutenyl group, 4-hebutenyl 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-hebutenyl group, 2-methyl-2-hebutenyl group, 2-methyl-2-cyclohexenyl group, 3-methyl-2-cyclohexenyl group, geranyl group, isogeranyl group Examples include a neryl group, a lapandulyl group, a 6-methylgeranyl group, a 1-methylgeranyl group, a 6-ethylgeranyl group, a perylyl group, a farnesyl group, a geranylgeranyl group, and a β-cyclogeranylgeranyl group.

The groups in the structural unit (I[) include 2.3-epoxypropyl group, 2.3-epoxybutyl group, 3.4-epoxybutyl group, 23-epoxy-2-methylpropyl group, 2-methyl- 2,3-epoxybutyl group, 3-methyl-2,3-epoxybutyl group, 2,3-epoxyheptyl group, 5.6-epoxyhebutyl group, 3-methyl-2,3-epoxybutyl group, 4
-Methyl-2,3-epoxyheptyl group, 4-methyl-
Examples include 5,6-epoxyheptyl group.

Suitable examples of the alkokino carbonyl group represented by Yl in the structural unit (I[[) include a methoxycarbonyl group,
Examples include ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentanoxycarbonyl group, hexanoxycarbonyl group, heptanoxycarbonyl group, and cyclohexanoquinecarbonyl group.

x5, s1, x7, x”, x in structural unit (■)
It is preferable that @ and XIO are each hydrogen atoms.

Further, n in the structural unit (IV) is preferably 0 or l.

Polymer (A) comprises acrylic acid or its ester which may be substituted with an alkyl group at the α-position, and structural unit C.
A polymer is obtained by copolymerization with a comonomer forming the structural unit (TV') or copolymerization of the acrylic acid or its ester with a comonomer forming the structural unit (II[) and a comonomer forming the structural unit (ff). , then the polymer and the group Y
1 and an alcohol having a group Y3, or the acrylic acid derivative forming the structural unit (I) and the acrylic acid derivative forming the structural unit (n) are reacted with the structural unit CW''). It can be produced by copolymerization with a comonomer forming the structural unit (III) or copolymerization of these acrylic acid derivatives with a comonomer forming the structural unit (III).

As the acrylic acid derivative forming the structural unit (I),
Allyl methacrylate, allyl acrylate, 2 (or 3)-butenyl methacrylate, 2 (or 3)-butenyl acrylate, 2-methyl 2-propenyl methacrylate, 2-methyl-2-propenyl acrylate,
2 (or 3 or 4)-hebutenyl methacrylate,
2 (or 3 or 4)-hebutenyl 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, 1.1 (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=hebutenyl methacrylate, 2 (or 3) Acrylic acid derivatives in which alcohol residues are chained, such as -methyl-2-heptenyl acrylate, 2 (or 3)-methyl-2-cyclohexenyl methacrylate, 2 (or 3)-methyl-2 - Acrylic acid derivatives having a cyclic alcohol residue such as cyclohexenyl acrylate; geranyl methacrylate, geranyl acrylate, neryl methacrylate, neryl acrylate, isogeranyl methacrylate, isogeranyl acrylate, lapanduryl methacrylate, lavanduryl acrylate, 6 - Non-conjugated double bonds such as methylgeranyl methacrylate, 6-methylgeranyl acrylate, l-methylgeranyl methacrylate, 1-methylgeranyl acrylate, 6-ethylgeranyl methacrylate, 6-ethylgeranyl acrylate, perylyl methacrylate, perillyl acrylate, etc. Esters of a chain or cyclic terpene alcohol with two acrylic acid or methacrylic acid: farnesyl methacrylate, farnesyl acrylate, geranylgeranyl methacrylate, geranylgeranyl acrylate, β-cyclogeranylgeranyl methacrylate,
Examples include esters of chain or cyclic terpene alcohols having three or more non-conjugated double bonds and acrylic acid or methacrylic acid, such as β-cyclogeranylgeranyl acrylate. 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 methods of obtaining alcohol as raw materials. This is preferable from the viewpoint of ease of ester synthesis.

Further, examples of the acrylic acid derivative 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-epoxyhebutyl methacrylate, 5.6-epoxyhebutyl methacrylate, 2.3-epoxyhebutyl acrylate,
5.6-Epoxy hebutyl acrylate, 2 (or 3
)-methyl-2,3-epoxybutyl methacrylate,
Examples include 2 (or 3)-methyl-2,3-epoxybutyl acrylate, 4-methyl-2,3-epoxybutyl methacrylate, and 4-methyl-5,6-epoxybutyl 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 (II[) include methacrylic acid: methyl methacrylate, ethyl methacrylate,
Methacrylic acid alkyl esters such as propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, amyl methacrylate, cyclohexyl methacrylate; acrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic Examples include alkyl acrylates such as pentyl acrylate, hexyl acrylate, amyl acrylate, and cyclohexyl acrylate; substituted styrenes such as methacrylic amide, acryl amide, styrene, and α-methylstyrene; The hydrogen atom in the structural unit (I [
-Norbornene-2,3-dicarboxylic anhydride, 7-oxa-5-methyl-5-norbornene-2,3-dicarboxylic anhydride, 7-oxa-5-ethyl-5-norbornene-2,3-dicarboxylic anhydride Acid anhydride, 4-methyl-7-
Oxa-5-norbornene-2,3-dicarboxylic anhydride, 14-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-saikutahid mouth-1
, 4: 5.8-dioxanaphthalene-2,3-dicarboxylic anhydride, 1.2°3.4,4a, 5.8,8a-
Octahydro-1,4: Acid anhydrides such as 5,8-dimethanonaphthalene-2,3-dicarboxylic anhydride and 3-methyl-5-norbornene-2,3-dicarboxylic anhydride can be mentioned. Among these, maleic anhydride,
5-norbornene-2,3-dicarboxylic anhydride, 7-
Oxa-5-norbornene-2,3-dicarboxylic acid is preferred from the viewpoint of ease of synthesis.

The polymer (^) has a number average molecular weight of 1.0 in terms of polystyrene determined by gel permeation chromatography.
Those in the range of 00 to 2,000,000 are preferred. The polymer (A) has a number average molecular weight of 100,000 to 1.
More preferably, it is in the range of 500,000.

Examples of the compound (B) include benzaldehyde, benzophenone, or derivatives thereof which may have a substituent, and specifically, the following general formula (V), general formula (V
T) or the general formula (■).

15 [In the formula, X mouth, x eye, X13, X14.115, xll
l, X17X11 and x-th each represent a hydrogen atom, an alkyl group or alkoxy group having 7 or less carbon atoms, or a halogen atom, and X! O,X! I, X″! x! Ko, x
14 and Xts each represent a hydrogen atom or a halogen atom. l is 0.1 or 2. Preferred compounds (B) include benzophenone; 3(or 4)-methylbenzophenone, 3(or 4)-methoxybenzophenone, 3.3' (or 4°4°)
-dimethylbenzophenone, 3,3° (or 4°4°
)-dimethoxybenzophenone, 2.3 (or 2.4
)-chlorobenzophenone, 3,4.5-) substituted benzophenones such as dimethoxybenzophenone, 3-benzoylbenzophenone; 3 (or 4)-methylbenzoyl-3° (or 4°)-methylbenzophenone;
(or 4)-Methoxybenzoyl-3° (or 4゛)-methoxybenzophenone, 3゜3-dibenzoylbenzophenone, meta-substituted benzophenones such as 1,3.5-)ribenzoylbenzene, benzaldehyde: 3 (or 4) Substituted benzaldehydes such as -methylbenzaldehyde, 3 (or 4)-methoxybenzaldehyde, 3,4-dimethylbenzaldehyde, and 3,4-dimethoxybenzaldehyde can be mentioned.

Among these, benzaldehyde, benzophenone, 3benzoylbenzophenone, 3.3'-9benzoylbenzophenone and 1,3.5-tribenzoylbenzene are preferred from the viewpoint of ease of synthesis, and 3-benzoylbenzophenone and 1 , 3.5-) Ribenzoylbenzene has good photoreactivity and can increase the difference in unevenness and the difference in refractive index between exposed areas and non-exposed areas,
This is particularly preferred because the produced pattern has high organic solvent resistance and high heat resistance.

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

The composition ratio of polymer (A) and compound (B) is 10:1 to
The range of 1:10 (weight ratio) is preferable, and 2:1-1.2
(weight ratio) is more preferable. The ratio of the structural unit (1) possessed by the polymer (A) to the compound (B) is 101 to 1
:20 (molar ratio) is preferable, and the range is 5:1 to 110 (
Molar ratio) 4) range is more preferable.

According to the present invention, another object of the above is to create a pattern using the photosensitive resin composition described above, which is characterized by comprising the following steps (a), (b) and (viii). &Achieved by providing law.

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

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

(c) Step of removing unreacted compound (B) from the thin film.

In the above 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 barcode method, a spin code method, etc. . The solvent is removed from the thin film by subjecting the thin film to vacuum treatment or heat treatment as required.

The method for forming the thin film is selected depending on 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 it is small, a bar code method or a spin code method is used.

(B) Process < ([+) In the process, the thin film is partially irradiated with ultraviolet rays having a wavelength of 200 to 450 nm in accordance with a desired pattern. As a result, the structural unit (I) and the compound (B) undergo a photoreaction. The light source is a high pressure mercury lamp, N
, gas laser, He-Cd laser, etc. are used.

As a method for forming a desired pattern, a mask exposure method using a photomask, a three-beam interference exposure method, a laser beam direct writing method, etc. are employed.

The unreacted compound (B) in step (c) following step (CI) is removed by heat treatment of the thin film at a temperature in the range of 20 to 120°C for 15 to 30 hours under reduced pressure (hereinafter, this is referred to as preheat treatment). ) and then heat-treated at a temperature in the range of 105 to 230° C. for 15 minutes to 40 hours under normal pressure (hereinafter referred to as post-heat treatment), or preheat-treated, and then a thin film of the photosensitive resin composition. The strength is 1 (1-4
0wY/cm” and the wavelength is 200 to 4
This is preferably carried out by irradiating ultraviolet light in the range of 50 ni for 30 seconds to 10 minutes. As a result, a pattern having a desired refractive index difference and unevenness difference is obtained. Since the structural unit (1), structural unit (n), and structural unit OV) included in the pattern are thermally crosslinked, the pattern has high organic solvent resistance and heat resistance. The above post-heat treatment is preferably carried out at a temperature in the range of 150 to 200°C for 1 to 5 hours, or more preferably at a temperature in the range of 110 to 140°C for 10 to 25 hours.

Further, it is preferable to carry out the above-mentioned pre-heat treatment, then carry out the post-heat treatment and then irradiate the pattern with ultraviolet rays, since this allows a pattern to be further improved in organic solvent resistance and heat resistance. Note that when the above preheat 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 when the above post heat treatment is omitted.

Patterns such as a guiding waveguide, a diffraction grating, a grating lens, a Fresnel lens, a hologram lens, etc. can be produced from a photosensitive resin composition by the above method.

Further, by doping a photosensitive resin composition with various nonlinear optical materials, a leading waveguide having a nonlinear effect can be produced. These patterns have excellent optical clarity, organic solvent resistance, and heat resistance.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 N! to the reaction vessel! (2-butenyl methacrylate after substitution)
70g, methyl methacrylate log, 2.3-epoxypropyl methacrylate 71g 1 maleic anhydride 9
8g of azobisisobutyronitrile, 600mg of azobisisobutyronitrile, and 90h12 of dioxane were charged, the tube was sealed and heated in a water bath at 53°C for 24 hours to perform a polymerization reaction. The resulting reaction solution was poured into 4 ρ of methanol to precipitate the product,
By drying, 150 g of polymer (A) was obtained. This polymer (A) is a copolymer with a molar ratio of 2-butenyl methacrylate, methyl methacrylate, 2.3-epoxypropyl methacrylate, and maleic anhydride of 1:2:1:1 from the results of NMR measurements. was confirmed. Further, the number average molecular weight of this polymer (A) in terms of polystyrene determined by gel permeation chromatography was 250.000. The above polymer (A) 1
A composition consisting of 0 parts of 3-benzoylbenzophenone and 6 parts of 3-benzoylbenzophenone was dissolved in toluene, and the resulting solution was used to form a thin film (thickness: 1.5 μm) on a glass substrate by spin coding.
m) was formed. This thin film was passed through a photomask with lines and spaces with a period of 35 g of pus at a rate of 25 m1/c.
m" ultraviolet rays for 120 seconds. After irradiation, the photomask was removed and dried at 100°C and 0.2 mmHg in a vacuum dryer.
Preheat treatment was performed for 20 hours under the following conditions. After that, the entire surface of the thin film was irradiated with ultraviolet rays of 40 m1/am'' for 7 minutes, and then post-heated at 120°C and normal pressure for 2 hours to remove unreacted compound (B) and refract. A diffraction grating pattern having a difference in index and a difference in unevenness was fabricated.

The diffraction efficiency of this diffraction grating was 33% for light with a wavelength of 633 nm. The diffraction grating was left in 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 refractive index of this diffraction grating did not change.

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

Examples 2 to 9 Photosensitive resin compositions consisting of the polymer (A) and compound (B) shown in Table 1 were prepared in the same manner as in Example 1, and photosensitive resin compositions having the compositions shown in Table 1 were prepared. A diffraction grating was produced using the same resin composition under the same conditions as in Example 1.

When the same organic solvent resistance and heat resistance tests as in Example 1 were conducted using the diffraction gratings prepared in each example, the diffraction efficiency did not change in any of the diffraction gratings.

In Table 1, parts indicate parts by weight.

Below is the margin Example 1O 10 parts of polymer (A) with the same composition as in Example 1 and 3
- Dissolve a composition consisting of 6 parts of benzoylbenzophenone in toluene, and use the resulting solution to coat 1 lll (thickness 1.5 μm) on a glass substrate by a spin code method.
was formed. This thin film was passed through a photomask with a 35μ-period line and space at 25aI/cm.
After irradiation, the photomask was removed and heat treated in a vacuum dryer at 110°C and 0.2 msHg for 20 hours. After that, the entire surface of the N film was exposed to ultraviolet rays of 25 mT/am. was irradiated for 5 minutes to remove unreacted compound (B), thereby producing a diffraction grating pattern having a difference in refractive index and a difference in unevenness.

The diffraction efficiency of this diffraction grating was 30% for light having a wavelength of 633n-, and like the diffraction grating of Example 1, the organic solvent resistance and heat resistance were good.

Example 11 After replacing ytWl in the reaction vessel, geranyl methacrylate 39
g, 26 g of 2,3-evoquinopropyl methacrylate
, methyl methacrylate 38g, maleic anhydride 40g
, azobisisobutyronitrile 135B and dioxane 450mC were charged, the tube was sealed and heated in a water bath at 55°C for 24 hours to perform a polymerization reaction. The resulting reaction solution was poured into methanol 1512 to precipitate the product,
60 g of polymer (A) was obtained from the drying process. The results of NMR measurements show that this polymer (A) is a copolymer with a molar ratio of geranyl methacrylate, 2,3-epoxypropyl methacrylate, methyl methacrylate, and maleic anhydride of 1:1:2:1. confirmed. Further, the number average molecular weight of this polymer (A) in terms of polystyrene determined by gel permeation chromatography was 300.000. A composition consisting of 10 parts of the above polymer (A) and 8 parts of 1,3,5-tribenzoylbenzene was dissolved in toluene, and the resulting solution was used to coat a thin 1j ( Thickness 1.
5μ■) was formed and irradiated with ultraviolet rays through a photomask under the same conditions as in Example 1. Thereafter, unreacted compound (B) was removed by pre-heat treatment, post-heat treatment and ultraviolet irradiation in the same manner as in Example 1, and a diffraction grating pattern having a difference in refractive index and a difference in unevenness was produced. .

Similar to the diffraction grating of Example 1, this diffraction grating had good organic solvent resistance and heat resistance.

Comparative Example 2 - The same method as in Example 1 using a photosensitive resin composition consisting of 10 parts of a copolymer with a molar ratio of butenyl methacrylate to methyl methacrylate of 1:3 and 6 parts of 3-benzoylbenzophenone. A diffraction grating was made using

The diffraction efficiency of this diffraction grating was 30% for light with a wavelength of 633 nm. When the diffraction grating was heated at 150° C. (normal pressure) for 4 hours, the diffraction grating was deformed and the diffraction efficiency decreased to 25%.

[Effects of the Invention] According to the present invention, a pattern having a surface relief structure in which the exposed part of the photosensitive resin has a higher refractive index and greater thickness than the unexposed part, and has excellent organic solvent resistance and heat resistance. A photosensitive resin composition is obtained that provides the following properties. Furthermore, a method for producing the above-mentioned pattern using the photosensitive resin composition and a pattern produced using the photosensitive resin composition are also obtained.

Claims (1)

[Claims] 1. The following general formula (I) (I)▲ Numerical formulas, chemical formulas, tables, etc.▼ [In the formula, X^1 represents a hydrogen atom or an alkyl group, and Y
^1 represents a cycloalkenyl group or a group represented by the following general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available▼. 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 (I
I) (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^2 represents a hydrogen atom or an alkyl group, and Z
^2 represents a divalent hydrocarbon group, and 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 (I
II) (III)▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X^3 represents a hydrogen atom or an alkyl group, and Y
^2 represents a phenyl group, an alkoxycarbonyl group or a carbamoyl group, and the hydrogen atom in general formula (III) may be substituted with a fluorine atom. ] 0 to 97 mol% of structural units represented by the following general formula (IV) (IV) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula,
^5, X^6, X^7, X^8, X^9 and X^1^
0 represents a hydrogen atom or an alkyl group, and n is 0
An integer between 3 and 3. ] A polymer having 1 to 97 mol% of structural units represented by (A
) and a compound (B) selected from the group consisting of aromatic aldehydes and aromatic ketones that may have substituents. 2. A pattern produced from the photosensitive resin composition according to claim 1. 3. (a) The following general formula (I) (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, X^1 represents a hydrogen atom or an alkyl group, and Y
^1 represents a cycloalkenyl group or a group represented by the following general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available▼. 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 (I
I) (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^2 represents a hydrogen atom or an alkyl group, and Z
^2 represents a divalent hydrocarbon group, and 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 (I
II) (III)▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X^3 represents a hydrogen atom or an alkyl group, and Y
^2 represents a phenyl group, an alkoxycarbonyl group or a carbamoyl group, and the hydrogen atom in general formula (III) may be substituted with a fluorine atom. ] 0 to 97 mol% of structural units represented by the following general formula (IV) (IV) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula,
^5, X^6, X^7, X^8, X^9 and X^1^
0 represents a hydrogen atom or an alkyl group, and n is 0
An integer between 3 and 3. ] A polymer having 1 to 97 mol% of structural units represented by (A
) and a compound (B) selected from the group consisting of aromatic aldehydes and aromatic ketones which may have substituents; (b) forming a thin film as desired in the thin film; (c) removing unreacted compound (B) from the thin film;
A pattern manufacturing method characterized by providing.