JP2003246930A - Radiation-sensitive refractive-index variable composition and method for varying refractive-index - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive and refractive-index variable composition capable of varying the refractive-index of a material by a simple method, forming a thick film, imparting a sufficient large value of a varied refractive- index difference and affording a stable refractive-index pattern or an optical material without relying on service conditions thereafter. <P>SOLUTION: The radiation-sensitive and refractive-index variable composition comprises (A) a degradable compound, (B) a nondegradable compound selected from the group consisting of a ladder type polysilsesquioxane, its hydrolyzate and a condensate thereof and having a lower refractive-index than that of the degradable compound (A), (C) a radiation-sensitive degrading agent and (D) a stabilizer. The components (C) and (A) in a part exposed to radiation are degraded to cause a difference between the part exposed to the radiation and a part unexposed to the radiation in the refractive index by exposing the composition through a pattern mask to the radiation. Thereby, the pattern having the different refractive-index is formed. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a radiation-sensitive refractive index changing composition, a method for forming a refractive index pattern, a refractive index pattern and an optical material. More specifically, a novel radiation-sensitive refractive index changing composition applied to the fields of optoelectronics and displays, a refractive index pattern forming method,
It relates to a refractive index pattern and an optical material.

[0002]

2. Description of the Related Art At present, which is referred to as a multimedia society, there is a great demand for a graded index type optical molded article composed of different refractive index regions. As such an example, not only an optical fiber for transmitting information, but also an optical diffraction grating having a periodic refractive index change, an optical memory in which information is written by a portion having a different refractive index, an optical integrated circuit having a fine refractive index pattern, etc. Examples include an optical coupling element, a light control element, a light modulation element, and a light transmission element.

Incidentally, the term "gradient distribution type optical molding" as used herein means that the refractive index is continuously distributed in a molding such as a GI type optical fiber (hereinafter referred to as GRIN optical molding). It refers to both cases where the distribution shape of the refractive index is discontinuous, such as an optical diffraction grating and an SI type optical waveguide.

The GRIN optical molded product has been attracting attention as a next-generation optical molded product. For example, G with a parabolic refractive index reduction from the central axis of the optical fiber core to the periphery
The I-type optical fiber enables transmission of a large amount of information, and the GRIN lens, in which the refractive index changes continuously in the lens, has features such as having refractive power even on a flat surface and not causing spherical aberration, It is applied to reading lenses used in copiers, spherical lenses that connect fibers, and microlenses.

Many proposals have been made so far as a method for producing the GRIN optical molded body as described above. For example, disperse low molecular weight or monomer in polymer,
A method of obtaining a GI type optical fiber by continuously distributing the concentration is disclosed in Japanese Patent Laid-Open No. 9-133813,
JP-A-8-336911, JP-A-8-33760
No. 9, JP-A-3-192310, JP-A-5-
No. 60931, WO93 / 19505 and WO94 / 04949. Further, JP-A-62-25705 discloses that a GI type rod-shaped optical molding or an optical fiber is obtained by copolymerizing two or more kinds of vinyl monomers having different refractive indexes and reaction ratios with light. Further, JP-A-7-56026 discloses that a polymer A having a photoreactive functional group is formed, a compound B having a lower refractive index than A is diffused into A, and a concentration distribution of B is formed. It discloses a method of reacting A and B with light to obtain a refractive index distribution.

Several methods for producing GRIN optical moldings of inorganic materials have also been proposed. For example, low refractive index thallium having a low refractive index is added to rod-shaped glass containing silicon or lead as a main component. This is a method of immersing in a melt containing potassium and forming a concentration distribution of potassium by ion exchange to form a GI type rod.

The GRIN lens can be similarly obtained by applying the above-mentioned method to a short rod, that is, a lens-shaped optical molded body. Alternatively, the GI type rod produced by the above method may be sliced.

Further, as a method for producing an optical molded body having a fine pattern of refractive index such as the above-mentioned optical diffraction grating, optical integrated circuit, etc., a photochemical reaction is induced in the molded body by light irradiation, and the refraction associated therewith is induced. A technique for obtaining a rate change is known. For example, in the case of an inorganic material, a method of irradiating a glass doped with germanium with light to change the refractive index and producing an optical diffraction grating can be mentioned. In addition, in organic materials, it is known as photochromic reaction or photobleaching, and a material in which low molecular weight photoactive photoactive molecules are dispersed in a polymer is irradiated with laser light to induce a change in the refractive index, which causes optical diffraction. A technique for forming a lattice is disclosed in Japanese Patent Laid-Open No. 7-92313. More recently, it has been proposed by JP-A-9-178901 to apply this technique to the production of GRIN optical moldings. This method takes advantage of the fact that the light radiated to the molded body is absorbed and the strength is weakened, and a continuous refractive index distribution in the depth direction is given to the irradiation.

However, in the refractive index distribution obtained by the above-mentioned conventional materials, the maximum refractive index difference is 0.0 at most.
It is about 01 to 0.02, and it is difficult to achieve a further large refractive index distribution for the purpose of preventing optical loss and suppressing circuit malfunction.

Also, after the refractive index distribution is formed once, if it is used under the condition that light near the wavelength used for changing the refractive index passes, the phenomenon that the refractive index gradually changes and deteriorates occurs. It could not be prevented.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned actual situation in the prior art.

That is, an object of the present invention is to change the refractive index of a material by a simple method, and the changed refractive index difference becomes a sufficiently large value, and a stable refractive index pattern is obtained irrespective of the subsequent usage conditions. Another object of the present invention is to provide a radiation-sensitive and refractive index changing composition which can be used as an optical material.

Another object of the present invention is to provide a radiation-sensitive refractive index changing composition which can be easily formed by coating and can be formed into a thick film without cracks.

Another object of the present invention is to form fine pores by irradiation of radiation, to stably maintain the fine pores formed, and to have a strong film strength despite having a large number of fine pores. It is an object of the present invention to provide a radiation-sensitive refractive index changing composition that provides a provided refractive index pattern.

Another object of the present invention is to provide a method for forming a refractive index pattern from the above composition of the present invention.

Still another object of the present invention is to provide a refractive index pattern or optical material produced by the above method of the present invention.

Further objects and advantages of the present invention will be apparent from the following description.

[0018]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) a degradable compound, (B) a ladder-type polysilsesquioxane, and a hydrolyzate thereof. And a non-decomposable compound selected from the group consisting of condensates thereof and having a refractive index lower than that of the decomposable compound (A),
The present invention is achieved by a radiation-sensitive refractive index changing composition, which comprises (C) a radiation-sensitive decomposition agent and (D) a stabilizer.

The above objects and advantages of the present invention are secondly
(A) a decomposable compound, (B) a ladder-type polysilsesquioxane, a non-decomposable compound selected from the group consisting of a hydrolyzate and a condensate thereof and having a refractive index lower than that of the decomposable compound (A), A radiation-sensitive refractive index changing composition containing (C) a radiation-sensitive decomposing agent and (D) a stabilizer is irradiated with radiation and then heated to stabilize the unexposed portion of the stabilizer (D).
And a decomposable compound (A) are reacted with each other.

Thirdly, the above objects and advantages of the present invention are as follows.
A non-decomposable compound selected from the group consisting of (A) decomposable compound, (B) ladder-type polysilsesquioxane, its hydrolyzate and its condensate and having a lower refractive index than the decomposable compound (A); (C) The composition for changing refractive index containing the radiation-sensitive decomposing agent is irradiated with radiation through a pattern mask, and then (D) is treated with a stabilizer to treat the unexposed portion (A).
It is achieved by a refractive index pattern forming method, which comprises reacting a decomposable compound with a stabilizer (D).

Fourthly, the above objects and advantages of the present invention are as follows.
A non-decomposable compound selected from the group consisting of (A) decomposable compound, (B) ladder-type polysilsesquioxane, its hydrolyzate and its condensate and having a lower refractive index than the decomposable compound (A); (C) A refractive index characterized by irradiating a refractive index-changing composition containing a radiation-sensitive decomposing agent with radiation through a pattern mask, followed by heat treatment to decompose a decomposable polymer in an unexposed area. This is achieved by a patterning method.

The above objects and advantages of the present invention are, fifthly, as follows.
This is achieved by the refractive index pattern formed by the above refractive index pattern forming method.

Sixth, the above objects and advantages of the present invention are as follows.
This is achieved by an optical material formed by the above refractive index pattern forming method.

In the present invention, the "refractive index pattern" means a gradient index material composed of regions having different refractive indexes.

Each component of the refractive index changing material used in the refractive index pattern forming method of the present invention will be described in detail below.

(A) Degradable Compound The (A) degradable compound used in the present invention may be an acid-decomposable compound or a base-decomposable compound, and its refractive index is preferably 1.5 to 1. It is 9. The weight average molecular weight of the decomposable compound (A) is preferably 100 to
500,000, more preferably 100 to 300,0
00.

As the acid-decomposable compound, the following formulas (1) to
Examples thereof include compounds having at least one structure selected from the group consisting of the structures represented by (8). These compounds may be used alone or in combination of two or more.

[0028]

[Chemical 16]

(In the formula (1), R ¹ is an alkylene group, an alkylenearylenealkylene group or an arylene group, and R ² is an alkylene group, an alkylenearylenealkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group. .)

[0030]

[Chemical 17]

(In the formula (2), M is Si or Ge.
And R ³ is an alkylene group, an alkylenearylene alkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group, and R ⁴ is an oxygen atom, an alkylene group, an alkylenearylenealkylene group, an arylene group or a single bond, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a thioalkyl group, and m is an integer of 0 to 2. )

[0032]

[Chemical 18]

(In the formula (3), R ⁹ and R ¹⁰ are each independently an alkylene group, an alkylenearylenealkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group.)

[0034]

[Chemical 19]

(In the formula (4), R ¹¹ is an oxyalkylene group or a single bond, and R ¹² is a hydrogen atom, an alkyl group, an alkylenearylenealkylene group or an aryl group.)

[0036]

[Chemical 20]

(In the formula (5), R ¹³ is a hydrogen atom, an alkyl group or an aryl group.)

[0038]

[Chemical 21]

(In the formula (6), R ¹⁴ is an alkylene group or the following formula (6) -1, (6) -2 or (6)-
It is a structure represented by 3. )

[0040]

[Chemical formula 22]

(In the formula (6) -1, R ¹⁵ , R ¹⁶ and R
¹⁷ and R ¹⁸ are each independently a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a mercapto group, a carboxyl group, an alkoxyl group having 1 to 6 carbon atoms, and a carbon number. An alkylthio group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkoxyl group having 1 to 6 carbon atoms, a halogenated alkylthio group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, A mercaptoalkyl group having 1 to 6 carbon atoms, a hydroxyalkoxyl group having 1 to 6 carbon atoms, a mercaptoalkylthio group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms. )

[0042]

[Chemical formula 23]

(In the formula (6) -2, R ¹⁹ is an alkylene group.)

[0044]

[Chemical formula 24]

(In the formula (6) -3, R ²⁰ is an alkylene group.)

[0046]

[Chemical 25]

(In the formula (7), R ²¹ is an alkylene group, an alkylenearylenealkylene group, or an arylene group.)

[0048]

[Chemical formula 26]

(Wherein R ²² , R ²³ , R ²⁴ and R ²⁵ are independently of each other a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a mercapto group, Carboxyl group, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, halogenated alkyl group having 1 to 6 carbon atoms, halogenated alkoxyl group having 1 to 6 carbon atoms, halogen having 1 to 6 carbon atoms Alkylthio group,
C1-6 hydroxyalkyl group, C1-6 mercaptoalkyl group, C1-6 hydroxyalkoxyl group, C1-6 mercaptoalkylthio group, C6-10 aryl group or carbon Number 7-11
Is an aralkyl group. )

Examples of the base decomposable compound include compounds having at least one structure selected from the group consisting of structures represented by any of the following formulas (9) to (12). These compounds may be used alone or in combination of two or more.

[0051]

[Chemical 27]

(In the formula (9), R ²⁶ is an alkylene group, an aralkylene group or an arylene group, and R ²⁷ is an alkylene group, an aralkylene group, an arylene group, an alkylenearylenealkylene group, an alkylsilylene group or an alkylgermylene group. R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a thioalkyl group, and i and j are each independently 0 or 1.)

[0053]

[Chemical 28]

(In the formula (10), R ³² is an alkylene group, an aralkylene group or an arylene group, and R ³³ is an alkylene group, an aralkylene group, an arylene group, an alkylenearylenealkylene group, an alkylsilylene group or an alkylgermylene group. is there.)

[0055]

[Chemical 29]

(In the formula (11), R ³⁴ and R ³⁵ are each independently an alkylene group, an aralkylene group, an arylene group, an alkylenearylenealkylene group, an alkylsilylene group, or an alkylgermylene group.)

[0057]

[Chemical 30]

(In the formula (12), R ³⁶ and R ³⁷ are each independently an alkylene group, an aralkylene group, an arylene group, an alkylenearylenealkylene group, an alkylsilylene group or an alkylgermylene group.) All the above alkylenes The arylenealkylene group is, for example, independently of the following formula (13) or (1
The structure shown in 4) is mentioned.

[0059]

[Chemical 31]

(In the formula (13), R ³⁸ , R ³⁹ , R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 and R ⁴² ,
R ⁴³ , R ⁴⁴ and R ⁴⁵ are each independently a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxy group,
It is a thioalkyl group, an alkyl ester group, an alkyl thioester group, an aryl group, a cyano group or a nitro group. )

[0061]

[Chemical 32]

[0062] ((14) ^{wherein, R 46, R 47, R} 48 and R ⁴⁹ are each independently a hydrogen atom, a linear alkyl group or 6-10 aryl group having 1 to 6 carbon atoms, R ⁵⁰ ,
R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ and R ⁵⁷ are each independently a hydrogen atom, chlorine atom, bromine atom, hydroxyl group, mercapto group, alkoxy group, thioalkyl group, alkyl ester group, alkyl thioester. A group, an aryl group, a cyano group or a nitro group, A ¹ is —S—, —O—, —
_{SO 2 -, - CO -,} - COO -, - OCOO -, - C
H ₂ - or -C (R ⁵⁸⁾ ₂ - are shown and R ⁵⁸ is a chain alkyl group having 1 to 6 carbon atoms. )

As all of the above-mentioned arylene groups, for example, a structure represented by the following formula (15) can be mentioned independently.

[0064]

[Chemical 33]

(Here, R ^{59 to} R ⁶⁶ are independently of each other a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxy group, a thioalkyl group, an alkyl ester group, an alkylthioester group, an aryl group, a cyano group or Represents a nitro group, A ² is —S—, —O—, —SO ₂ —, —C
O -, - COO -, - OCOO -, - CH 2 - or -
C (R ⁶⁷ ) _2- is shown and R ⁶⁷ is a chain alkyl group having 1 to 6 carbon atoms. )

All of the above alkylsilylene groups include
Independently of each other, for example, a structure represented by the following formula (16) can be mentioned.

[0067]

[Chemical 34]

(Here, R ⁶⁸ , R ⁶⁹ , R ⁷⁰ and R ⁷¹ each independently represent a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and A ³ is -O
Represents an-, an alkylene group or an arylene group, and a represents an integer of 0 or 1. )

As all of the above-mentioned alkylgermylene groups, a structure represented by the following formula (17) can be mentioned, independently of each other.

[0070]

[Chemical 35]

(Wherein R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ each independently represent a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and A ⁴ is -O
Represents an alkylene group or an arylene group, and b represents an integer of 0 or 1. )

The alkylene groups in the above formulas (16) and (17) are each independently preferably a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, such as methylene, 1,2-ethylene, 1,3-trimethylene, 1,10-decamethylene, etc. can be mentioned, and these hydrogen atoms are, for example, chlorine atom, bromine atom, hydroxyl group, mercapto group, alkoxy group, thioalkyl group,
It may be substituted with an alkyl ester group, an alkyl thioester group, an aryl group or a cyano group.

The alkyl groups of all the above alkyl groups, alkoxy groups, thioalkyl groups, alkyl ester groups and alkyl thioester groups are, for example, independently of one another, for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Is preferred, and these hydrogen atoms are chlorine atoms,
It may be substituted with a bromine atom, a hydroxyl group, a mercapto group, an alkoxy group, a thioalkyl group, an alkyl ester group, an alkyl thioester group, an aryl group or a cyano group.

As all of the above aryl groups, independently of each other, for example, a phenyl group, a naphthyl group, an anthracenyl group or a biphenyl group, and a hydrogen atom thereof is a chlorine atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxy group,
Mention may be made of those substituted with a thioalkyl group, an alkyl ester group, an alkyl thioester group, a cyano group or a nitro group.

The chain alkyl group having 1 to 6 carbon atoms in the above (6) -1 and (8) may be linear or branched, for example, methyl group, ethyl group, n-propyl group. Group, i-propyl group, n-butyl group, i-butyl group,
Examples thereof include sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group and thexyl group.

The alkoxyl group having 1 to 6 carbon atoms may be linear or branched and includes, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-
Butoxy group, i-butoxy group, sec-butoxy group, t
Examples thereof include butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group and thexyloxy group.

The alkylthio group having 1 to 6 carbon atoms may be linear or branched, and examples thereof include methylthio group, ethylthio group, n-propylthio group, i-propylthio group and n-butylthio group. , I-butylthio group, sec
Examples thereof include -butylthio group, t-butylthio group, n-pentylthio group, neopentylthio group, n-hexylthio group and thexylthio group.

Examples of the halogenated alkyl group having 1 to 6 carbon atoms include, for example, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, chloromethyl group,
2-chloroethyl group, 3-chloropropyl group, 1-chloromethylethyl group, 4-chlorobutyl group, 2-chloromethylpropyl group, 5-chloropentyl group, 3-chloromethylbutyl group, 2-chloroethylpropyl group, 6-chlorohexyl group, 3-chloromethylpentyl group, 4-chloromethylpentyl group, 2-chloroethylbutyl group, bromomethyl group, 2-bromoethyl group, 3-bromopropyl group, 1-bromomethylethyl group, 4- Bromobutyl group,
2-bromomethylpropyl group, 5-bromopentyl group,
Examples thereof include a 3-bromomethylbutyl group, a 2-bromoethylpropyl group, a 6-bromohexyl group, a 3-bromomethylpentyl group, a 4-bromomethylpentyl group and a 2-bromoethylbutyl group.

The halogenated alkoxyl group having 1 to 6 carbon atoms includes, for example, trifluoromethoxy group, pentafluoroethoxy group, heptafluoropropoxy group, chloromethoxy group, 2-chloroethoxy group, 3-chloropropoxy group, 1- Chloromethylethoxy group, 4-chlorobutoxy group, 2-chloromethylpropoxy group, 5-chloropentyloxy group, 3-chloromethylbutoxy group, 2-chloroethylpropoxy group, 6-chlorohexyloxy group, 3-chloromethyl Pentyloxy group, 4-chloromethylpentyloxy group, 2-chloroethylbutoxy group,
Bromomethoxy group, 2-bromoethoxy group, 3-bromopropoxy group, 1-bromomethylethoxy group, 4-bromobutoxy group, 2-bromomethylpropoxy group, 5-bromopentyloxy group, 3-bromomethylbutoxy group,
Examples thereof include a 2-bromoethylpropoxy group, a 6-bromohexyloxy group, a 3-bromomethylpentyloxy group, a 4-bromomethylpentyloxy group and a 2-bromoethylbutoxy group.

Examples of the halogenated alkylthio group having 1 to 6 carbon atoms include a trifluoromethylthio group, a pentafluoroethylthio group, a heptafluoropropylthio group,
Chloromethylthio group, 2-chloroethylthio group, 3-chloropropylthio group, 1-chloromethylethylthio group,
4-chlorobutylthio group, 2-chloromethylpropylthio group, 5-chloropentylthio group, 3-chloromethylbutylthio group, 2-chloroethylpropylthio group, 6-chlorohexylthio group, 3-chloromethylpentyl Ruthio group, 4-chloromethylpentylthio group, 2-chloroethylbutylthio group, bromomethylthio group, 2-bromoethylthio group, 3-bromopropylthio group, 1-bromomethylethylthio group, 4-bromobutylthio group Group, 2-bromomethylpropylthio group, 5-bromopentylthio group, 3
-Bromomethylbutylthio group, 2-bromoethylpropylthio group, 6-bromohexylthio group, 3-bromomethylpentylthio group, 4-bromomethylpentylthio group,
A 2-bromoethyl butylthio group etc. can be mentioned.

Examples of the hydroxyalkyl group having 1 to 6 carbon atoms include hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 1-hydroxymethylethyl group, 4-hydroxybutyl group and 2-hydroxymethylpropyl group. Group, 5-hydroxypentyl group, 3-hydroxymethylbutyl group, 2-hydroxyethylpropyl group, 6-hydroxyhexyl group, 3-hydroxymethylpentyl group, 4-hydroxymethylpentyl group, 2-
A hydroxyethyl butyl group etc. can be mentioned.

Examples of the mercaptoalkyl group having 1 to 6 carbon atoms include mercaptomethyl group, 2-mercaptoethyl group, 3-mercaptopropyl group, 1-mercaptomethylethyl group, 4-mercaptobutyl group and 2-mercaptomethylpropyl group. Group, 5-mercaptopentyl group, 3-mercaptomethylbutyl group, 2-mercaptoethylpropyl group, 6-mercaptohexyl group, 3-mercaptomethylpentyl group, 4-mercaptomethylpentyl group, 2-
A mercaptoethyl butyl group etc. can be mentioned.

Examples of the hydroxyalkoxyl group having 1 to 6 carbon atoms include hydroxymethoxy group, 2-hydroxyethoxy group, 3-hydroxypropoxy group, 1-hydroxymethylethoxy group, 4-hydroxybutoxy group,
2-hydroxymethylpropoxy group, 5-hydroxypentyloxy group, 3-hydroxymethylbutoxy group, 2
Examples thereof include -hydroxyethylpropoxy group, 6-hydroxyhexyloxy group, 3-hydroxymethylpentyloxy group, 4-hydroxymethylpentyloxy group and 2-hydroxyethylbutoxy group.

As the mercaptoalkylthio group having 1 to 6 carbon atoms, for example, mercaptomethylthio group, 2-mercaptoethylthio group, 3-mercaptopropylthio group, 1
-Mercaptomethylethylthio group, 4-mercaptobutylthio group, 2-mercaptomethylpropylthio group, 5-
Mercaptopentylthio group, 3-mercaptomethylbutylthio group, 2-mercaptoethylpropylthio group, 6-
Mercaptohexylthio group, 3-mercaptomethylpentylthio group, 4-mercaptomethylpentylthio group, 2
-A mercaptoethyl butyl thio group etc. can be mentioned.

Examples of the aryl group having 6 to 10 carbon atoms include phenyl group, tolyl group, xylyl group, cumenyl group,
1-naphthyl group etc. can be mentioned.

As the aralkyl group having 7 to 11 carbon atoms,
Examples thereof include benzyl, α-methylbenzyl group, phenethyl group, naphthylmethyl group and the like.

A method for producing an acid-decomposable compound having the structures represented by the above formulas (1) to (7) in the present invention as a repeating unit is known.

The method for producing the compound having the structure represented by the above formula (1) is described in Polymer Bull. , 1.1
99 (1978), JP-A-62-136638,
EP 225,454, US806,597, JP-A-4-
It is disclosed in JP-A-303843, JP-A-7-56354 and the like.

The method for producing the compound having the structure represented by the above formula (2) is described in Macromolecules 2
9,5529 (1996), Polymer 17,1.
086 (1976) and JP-A-60-37549.

The method for producing the compound having the structure represented by the above formula (3) is described in Electrochem. So
c. , Solid State Sci. Techno
l. , 133 (1) 181 (1986), J. Image
ing Sci. , 30 (2) 59 (1986) and Macromol. Chem. , Rapid Comm
un. , 7, 121 (1986) and the like.

The method for producing the compound having the structure represented by the above formula (4) is described in US Pat. No. 3,894,253, JP-A-62-190211, JP-A 2-1.
46544, Macromol. Chem. , 2
3, 16 (1957), JP-A-63-97945, Polymer Sci. , A-1, 8, 2375
(1970), U.S. Pat. No. 4,247,611, EP41,657, JP-A-57-31674, JP-A-64-3647 and JP-A-56-1.
It is disclosed in Japanese Patent No. 7345.

The method for producing the compound having the structure represented by the above formula (5) is described in Prepr. Eur. Disc M
eet. Polymer Sci. , Strasbouw
rg, p106 (1978) and Macromol.
Chem. , 179, 1689 (1978) and the like.

The method for producing the compound having the structure represented by the above formula (6) is described in US Pat. No. 3,894,253, US Pat. No. 3,940,507 and JP-A-62-190211. It is disclosed in Japanese Patent Publication No.

The method for producing the compound having the structure represented by the above formula (7) is described in J. Am. Chem. Soc. , 5
4, 1579 (1932), J. Polym. Sc
i. 29, 343 (1958), J. Polym. S
ci. , Part A, Polym. Chem. , 25,
3373 (1958), Macromolecule
s, 25, 12, (1992), Macromolec
ules, 20, 705, (1997), Macrom
olecules, 21, 1925, (1998), M
acromol. Chem. , Rapid Commu
n. , 11, 83 (1990) and the like.

The compound having the structure represented by the above formula (8) is obtained by subjecting the compound represented by the following formula (8) -1 to cationic polymerization or anion in a solvent, if necessary in the presence of a molecular weight modifier. It can be produced by polymerization.

[0096]

[Chemical 36]

(Where R²⁰¹, R²⁰², R²⁰³And R
²⁰⁴Is defined as R in equation (8)^{twenty two}, R^{twenty three}, R ^{twenty four}And R^{twenty five}so
It is a group selected from the same groups as the defined groups. )

Further, the compound represented by the above formula (8) is
A compound represented by the following formula (8) -2, a following formula (8) -3
A compound represented by the following formula, and one or more compounds selected from the group consisting of other monomers, and the above formula (8)-
It may be a copolymer with the compound represented by 1. In this case, a compound represented by the following formula (8) -2, a compound represented by the following formula (8) -3, and one or more compounds selected from the group consisting of other monomers The total amount can be 100 parts by weight or less with respect to 100 parts by weight of the compound represented by the formula (8) -1.

[0099]

[Chemical 37]

(Here, R ²⁰⁵ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is represented by R ²⁰⁶ , R ^{20 7} , R ²⁰⁸ , and R ^209.
And R ²¹⁰ are each independently a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a mercapto group, a carboxyl group, an alkoxyl group having 1 to 6 carbon atoms, and a carbon number 1 To C6 alkylthio group, C1 to C6 halogenated alkyl group, C1 to C6 halogenated alkoxyl group, C1 to C6 halogenated alkylthio group, C1 to C6 hydroxyalkyl group, carbon C1-C6 mercaptoalkyl group, C1-C6 hydroxyalkoxyl group, C1-C6 mercaptoalkylthio group, C6-C10 aryl group, C7
~ 11 aralkyl groups, or R ²⁰⁶ , R
Any two of ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ and R ²¹⁰ may be bonded to each other to form a 4- to 7-membered ring together with the carbon atom to which they are bonded. )

[0101]

[Chemical 38]

(Here, R ²¹¹ and R ²¹² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms.
A halogenated alkyl group having 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a mercaptoalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an ethyleneoxy repeating unit. 1 to 5 (polyethylene glycol) ethyl groups, propyleneoxy repeating units 1 to 5 (polypropylene glycol) propyl groups, repeating units 1 to 5 (polyethylene sulfide) ethyl groups, repeating units 1 to 5 (polypropylene Sulfide) propyl group and the like. )

Examples of other monomers other than the above include glyoxal, succinaldehyde, glutaraldehyde, malealdehyde, 1,8-octanedialdehyde,
m-phthalaldehyde, p-phthalaldehyde, 2,3
-Naphthalene dicarboxaldehyde, 2,3-anthracene dicarboxaldehyde, 9,10-anthracene dicarboxaldehyde, 4,4'-bisbenzaldehyde, 2,5-dimethoxy-1,4-dicarboxaldehyde, 2,2 '-(ethylenedioxy) dibenzaldehyde, 2,2'-biphenyldicarboxaldehyde, bis (2-formylphenyl) ether, 6,6'-dihydroxy-5,5'-dimethoxy- [1, 1'-biphenyl] -3,3'-dicarboxaldehyde, a compound having two aldehyde groups in one molecule, salicylaldehyde chromium complex, aluminum formyl acetate, (1,1 ', 3', 1 )) Terphenyl-2,6
2 ", 6" -tetracarbaldehyde, 2-hydroxybenzene-1,3,5-tricarbaldehyde, 1,2,
Examples include compounds having three or more aldehyde groups in one molecule such as 4,5-tetra (p-formylphenyl) benzene.

The hydrogen atom of these compounds has 1 carbon atom.
-10 alkoxyl group, C1-C10 halogenated alkyl group, C1-C10 halogenated alkoxyl group, C1-C10 halogenated alkylthio group, C1-C10 hydroxyalkyl group, carbon A mercaptoalkyl group having 1 to 10 carbon atoms, a hydroxyalkoxyl group having 1 to 10 carbon atoms, a mercaptoalkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and a repeating unit It is also possible to use a compound substituted with a (polyethylene glycol) ethyl group of 1 to 5 and a (polypropylene glycol) propyl group of which the repeating unit is 1 to 5 and the like.

Cationic polymerization and / or anionic polymerization for producing the compound having the structure represented by the above formula (8) is carried out by anionic polymerization catalysts, coordination anionic polymerization catalysts,
Alternatively, it can be carried out using a cationic polymerization catalyst. Representative examples of anionic polymerization catalysts or coordination anionic polymerization catalysts are alkali metals such as sodium and lithium; s
-Alkyl metal compounds such as butyl lithium; alkali metal complex compounds such as sodium / naphthalene; alkali metal alkoxides such as sodium methoxide; amines such as n-butylamine, diethylamine; ammonium stearate, quaternary ammonium such as tetrabutylammonium acetate. Salts: 4-valent organotin compounds such as dibutyltin dilaurate, tributyltin chloride and diethyltin dilaurate.

Typical examples of the cationic polymerization catalyst are tin tetrachloride, tin tetrabromide, titanium tetrachloride, aluminum trichloride, zinc chloride, boron trifluoride, boron trifluoride diethyl etherate, perchloric acid. , Acetyl perchlorate, p-toluene sulfonic acid, triethyloxonium tetrafluoroborate, triethyl aluminum, diethyl aluminum chloride and the like.

Examples of the polymerization solvent include aliphatic hydrocarbons such as hexane, heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as methylene chloride, ethylene chloride and carbon tetrachloride. A halogenated aromatic hydrocarbon such as chlorobenzene or orthodichlorobenzene can be used. These organic solvents may be used alone or in combination of two or more. It is preferable that these organic solvents are sufficiently dehydrated and purified.

The molecular weight modifier optionally made to coexist during the production of this polymer is preferably used by being uniformly dissolved or dispersed in the reaction system, and alcohol, carboxylic acid or the like can be used.

As the alcohol, for example, methyl alcohol, ethyl alcohol, hexyl alcohol, cyclohexyl alcohol, benzyl alcohol, etc. can be used, and as the carboxylic acid, formic acid, acetic acid, propionic acid, lauric acid, palmitic acid, benzoic acid, etc. can be used. An acid or the like can be used. The amount of the molecular weight regulator used is
It is adjusted according to the molecular weight of the desired polymer and can be easily determined experimentally.

The reaction temperature is preferably -200 ° C to 50 ° C.
The temperature is set to between 0 ° C and, in many cases, a temperature between -100 ° C and 30 ° C is more preferable in consideration of the freezing point and boiling point of the organic solvent. The reaction time is not particularly limited, but usually can be appropriately set within the range of 100 hours. After a predetermined polymerization time, for example,
The obtained reaction mixture is filtered, the obtained solid matter is washed with ion-exchanged water, and then vacuum dried to obtain the target compound having the structure represented by the above formula (8). it can. The hydroxyl group at the terminal of the hemiacetal-type molecule formed by the above-mentioned polymerization reaction is somewhat lacking in thermal stability. Therefore, if necessary, esterification, etherification, urethane formation, etc. Stability can be improved by blocking the molecular ends according to a method known as a blocking method.

Further, a method for producing a base-decomposable compound having a structure represented by the above formulas (9) to (12) as a repeating unit is also known.

A method for producing a compound having a structure represented by the above formula (9) is described in Macromol. Chem. , Ra
pid Commun. , 5, 151 (1984), M
acromol. Chem. , 189, 2229 (19
88), Macromol. Chem. , 187, 25
25 (1986), Polym. J. , 22,803
(1990) and the like.

The method for producing the compound having the structure represented by the above formula (10) is described in J. Polym. Sci. , 47,
1523 (1993), J. Appl. Polym. S
ci. 35, 85 (1985), J. Polym. S
ci. , Polym. Chem. Ed. , 22, 157
9 (1984), J. Polym. Sci. , Poly
m. Chem. Ed. , 14,655 (1976),
J. Polym. Sci. , Polym. Chem. E
d. , 17, 2429 (1979) and the like.

The method for producing the compound having the structure represented by the above formula (11) is described in J. Macromol. Sci. −
Chem. , A9, 1265 (1975) and the like.

The method for producing the compound having the structure represented by the above formula (12) is described in Polym. Bull. , 14, 85
(1985), Macromol. Chem. , 18
9, 1323 (1988) and the like.

(B) Non-decomposable Compound (B) The non-decomposable compound used in the present invention is a material that is stable to an acid or a base and is preferably highly optically transparent. The refractive index of the component (B) can be arbitrarily set and adjusted to a preferable value depending on the application. The refractive index n _B of the compound (B) is the decomposable compound (A).
It is particularly preferable that the refractive index n _A is smaller than the refractive index n _A , and that the relationship of the following formula (1) is satisfied. n _A −n _B ≧ 0.05. ． ． (1)

The non-decomposable compound (B) is selected from the group consisting of ladder-type polysilsesquioxane, its hydrolyzate and its condensate. These can be used as one kind or as a mixture of two or more kinds.

The ladder-type polysilsesquioxane is represented by the following formula (18)

[0119]

[Chemical Formula 39]

(Here, R _X represents a monovalent organic group, and R _Y
Represents a hydrogen atom or a monovalent organic group, and R _X and R _Y may be the same or different. Further, n is a positive integer corresponding to the molecular weight. )

Examples of the monovalent organic group in the above formula (18) include an alkyl group, an aryl group, an allyl group and a glycidyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and the like, preferably having 1 to 5 carbon atoms, and these alkyl groups may be chain-like or branched. Examples of the aryl group include a phenyl group, a naphthyl group and a tolyl group. Furthermore, these alkyl groups,
The hydrogen atom of the aryl group, the allyl group, or the glycidyl group is substituted with a halogen atom such as a chlorine atom or a bromine atom, a hydroxyl group, a mercapto group, an alkoxy group, a thioalkyl group, an alkyl ester group, an alkylthioester group, or an aryl group. Good.

The method for producing the compound having the structure represented by the above formula (18) is described in, for example, JP-A-56-157885, JP-A-57-40526, and JP-A-58-6.
No. 9217 is disclosed. These commercially available products include GR-100, GR-650, GR-908,
GR-950 (above, Showa Denko KK make) etc. can be mentioned.

As the component (B), not only the compound represented by the above formula (18) but also its hydrolyzate and condensate can be used. The hydrolysis reaction is carried out in the presence of water and an appropriate catalyst as described below.

Specifically, the compound represented by the above formula (18) is dissolved in a suitable organic solvent, and water is intermittently or continuously added to this solution. At this time, the catalyst is
It may be dissolved or dispersed in an organic solvent in advance, or may be dissolved or dispersed in water to be added.

The temperature for carrying out the hydrolysis reaction and / or the condensation reaction is usually 0 to 100 ° C, preferably 15 to 80 ° C.

Water for the hydrolysis and / or condensation of the compound represented by the above formula (18) is not particularly limited, but ion-exchanged water is preferably used.

The amount of water used is 0.25 to 3 mol, particularly 0.3 to 2.5 mol, per 1 mol of the total alkoxyl groups of the compound represented by the above formula (18). The amount is preferably

As the catalyst for carrying out hydrolysis and / or condensation of the compound represented by the above formula (18), a metal chelate compound, an organic acid, an inorganic acid, an organic base, an inorganic base or the like can be used.

Specific examples of the metal chelate compound used as the catalyst include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, and tri-i-propoxy mono (acetylacetoacetate). Nato) titanium, tri-n-butoxy mono (acetylacetonato) titanium, tri-se
c-butoxy mono (acetylacetonate) titanium,
Tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n-propoxybis (acetylacetonato) titanium, di-i-propoxybis (acetylacetonate) Titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonato) titanium, di-t-butoxy.
Bis (acetylacetonate) titanium, monoethoxy
Tris (acetylacetonate) titanium, mono-n-propoxy tris (acetylacetonate) titanium, mono-i-propoxy tris (acetylacetonate)
Titanium, mono-n-butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate). Titanium,

Triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) titanium, tri-n-butoxy mono (ethyl). Acetoacetate) titanium, tri-s
ec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Di-i-propoxy bis (ethylacetoacetate) titanium, di-n-butoxy bis (ethylacetoacetate) titanium, di-sec-butoxy bis (ethylacetoacetate) titanium, di-t.
-Butoxy bis (ethylacetoacetate) titanium,
Monoethoxy tris (ethylacetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, mono-i-propoxy tris (ethylacetoacetate) titanium, mono-n-butoxy tris (ethylacetoacetate). ) Titanium, mono-sec
-Butoxy-tris (ethylacetoacetate) titanium, mono-t-butoxy-tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate)
Titanium chelate compounds such as titanium, mono (acetylacetonato) tris (ethylacetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;

Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetyl) Acetonato) zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxy.
Bis (acetylacetonato) zirconium, di-n-
Propoxy bis (acetylacetonato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy.
Bis (acetylacetonato) zirconium, di-t-
Butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxy tris (acetylacetonato) zirconium, mono-i-propoxy.
Tris (acetylacetonate) zirconium, mono-
n-butoxy tris (acetylacetonato) zirconium, mono-sec-butoxy tris (acetylacetonato) zirconium, mono-t-butoxy tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium,

Triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy mono (ethylacetoacetate) zirconium, tri-n-butoxy mono (ethyl). Acetoacetate) zirconium, tri-sec-butoxy mono (ethylacetoacetate) zirconium, tri-t-butoxy mono (ethylacetoacetate) zirconium,
Diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) Zirconium, di-
sec-butoxy bis (ethylacetoacetate) zirconium, di-t-butoxy bis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) zirconium, mono-n-propoxy tris (ethylacetoacetate) zirconium , Mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-n-butoxy tris (ethylacetoacetate) zirconium, mono-se
c-butoxy tris (ethylacetoacetate) zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium,
Zirconium chelate compounds such as bis (acetylacetonato) bis (ethylacetoacetate) zirconium and tris (acetylacetonato) mono (ethylacetoacetate) zirconium;

Examples thereof include aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum.

Specific examples of the organic acid used as the catalyst include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid,
Decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, meritic acid,
Arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid,
Benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid Etc. can be mentioned.

Specific examples of the inorganic acid used as the catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.

Specific examples of the organic base used as a catalyst include, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, Examples thereof include diazabicyclooclan, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide and the like.

As the inorganic base used as a catalyst,
Examples thereof include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

Among these, it is preferable to use a metal chelate compound, an organic acid or an inorganic acid as a catalyst,
More preferably, it is a titanium chelate compound or an organic acid.

These compounds may be used alone or in combination of two or more as a catalyst.

The amount of the catalyst used is usually 0.001 to 10 parts by weight, preferably 0.0 to 100 parts by weight of the compound represented by the above formula (18) converted to SiO _2.
It is in the range of 1 to 10 parts by weight.

Further, it is preferable that after hydrolyzing and / or condensing the compound represented by the above formula (18), residual water and alcohols generated as a reaction by-product are removed. The component (B) has a weight average molecular weight of 500 to 500,0 in terms of polystyrene.
It is preferably 00, and more preferably 500 to 300,000.

The component (B) is preferably 10 to 95 parts by weight, and more preferably 10 to 90 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). Is more preferable, 20 to 90 parts by weight is further preferable, and 20 to 70 parts by weight is particularly preferable. When the component (B) is 10 parts by weight or less, the refractive index changing material tends to be brittle, and when it is 90 parts by weight or more, the obtained refractive index difference tends to be small.

(C) Radiation-sensitive degrading agent The radiation-sensitive degrading agent (C) used in the present invention can be a radiation-sensitive acid generator or a radiation-sensitive base generator. In this case, when an acid-decomposable polymer is used as the (A) decomposable polymer, a radiation-sensitive acid generator is used as the (C) radiation-sensitive decomposing agent, and base decomposition is performed as the (A) decomposable polymer. When a volatile polymer is used, it is preferable to use a radiation-sensitive base generator as the radiation-sensitive decomposing agent (C).

As the radiation-sensitive acid generator, for example, trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, sulfonic acid esters and the like can be used.

Examples of the above trichloromethyl-s-triazines include 2,4,6-tris (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2 -(4-chlorophenyl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (3-chlorophenyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(2-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) ) -4,6-Bis (trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (4-methylthiophenyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (3-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methylthiophenyl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (4-methoxynaphthyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(3-Methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy) -Β-styryl) -4,6-
Bis (trichloromethyl) -s-triazine, 2- (3
-Methoxy-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxy-β
-Styryl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (3,4,5-trimethoxy-β-
Styryl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (4-methylthio-β-styryl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (3-methylthio-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -4,6-bis (trichloromethyl) -s- Triazine, 2-piperonyl-4,6-
Bis (trichloromethyl) -s-triazine, 2- [2
-(Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-
Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2-
(4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine and the like.

Examples of the diaryliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfone. Nato, diphenyliodonium butyl tris (2,6-
Difluorophenyl) borate, diphenyliodonium hexyl tris (p-chlorophenyl) borate, diphenyliodonium hexyl tris (3-trifluoromethylphenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate,
4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium butyl tris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium hexyl tris ( p-chlorophenyl)
Borate, 4-methoxyphenylphenyliodonium hexyl tris (3-trifluoromethylphenyl) borate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-)
Butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-te
rt-Butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, bis (4-ter)
t-Butylphenyl) iodonium butyl tris (2,2
6-difluorophenyl) borate, bis (4-ter)
t-Butylphenyl) iodonium hexyl tris (p
-Chlorophenyl) borate, bis (4-tert-butylphenyl) iodonium hexyl tris (3-trifluoromethylphenyl) borate and the like can be mentioned.

Examples of the above triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate and triphenylsulfonium trifluoroacetate. Phenylsulfonium-p-toluenesulfonate, triphenylsulfonium butyl tris (2,6-difluorophenyl) borate, triphenylsulfonium hexyl tris (p-chlorophenyl) borate, triphenylsulfonium hexyl tris (3-trifluoromethylphenyl) borate , 4-
Methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfoniumbutyl tris (2,6-difluorophenyl) borate, 4-methoxyphenyldiphenylsulfonium hexyltris (p-chlorophenyl) borate, 4-
Methoxyphenyldiphenylsulfoniumhexyl tris (3-trifluoromethylphenyl) borate, 4-
Phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenylsulfonium butyl tris (2,
6-difluorophenyl) borate, 4-phenylthiophenyldiphenylsulfonium hexyl tris (p-
Chlorophenyl) borate, 4-phenylthiophenyldiphenylsulfoniumhexyl tris (3-trifluoromethylphenyl) borate, 4-hydroxy-1-
Naphthalenyldimethylsulfonium tetrafluoroborate, 4-hydroxy-1-naphthalenyldimethylsulfonium hexafluorophosphonate, 4-hydroxy-1-naphthalenyldimethylsulfonium hexafluoroarsenate, 4-hydroxy-1-naphthalenyldimethyl Sulfonium trifluoromethanesulfonate,
4-hydroxy-1-naphthalenyldimethylsulfonium trifluoroacetate, 4-hydroxy-1-naphthalenyldimethylsulfonium-p-toluenesulfonate, 4-hydroxy-1-naphthalenyldimethylsulfonium butyl tris (2,6 -Difluorophenyl)
Examples thereof include borate, 4-hydroxy-1-naphthalenyldimethylsulfoniumhexyltris (p-chlorophenyl) borate, 4-hydroxy-1-naphthalenyldimethylsulfoniumhexyltris (3-trifluoromethylphenyl) borate and the like.

Examples of the above quaternary ammonium salts include tetramethylammonium tetrafluoroborate,
Tetramethylammonium hexafluorophosphonate, tetramethylammonium hexafluoroarsenate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium-p-toluenesulfonate, tetramethylammoniumbutyltris (2,6- Difluorophenyl) borate, tetramethylammonium hexyl tris (p-chlorophenyl)
Borate, tetramethylammonium hexyl tris (3-trifluoromethylphenyl) borate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphonate, tetrabutylammonium hexafluoroarsenate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium Trifluoroacetate, tetrabutylammonium-p-toluenesulfonate, tetrabutylammoniumbutyltris (2,6
-Difluorophenyl) borate, tetrabutylammoniumhexyltris (p-chlorophenyl) borate, tetrabutylammoniumhexyltris (3-trifluoromethylphenyl) borate, benzyltrimethylammonium tetrafluoroborate, benzyltrimethylammonium hexafluorophosphonate, benzyltrimethylammonium Hexafluoroarsenate, benzyltrimethylammonium trifluoromethanesulfonate, benzyltrimethylammonium trifluoroacetate, benzyltrimethylammonium-p-toluenesulfonate, benzyltrimethylammonium butyl tris (2,6-difluorophenyl) borate, benzyltrimethylammonium hexyl tris (P-chloro Phenyl) borate, benzyltrimethylammonium hexyl tris (3-trifluoromethylphenyl) borate, benzyldimethylphenylammonium tetrafluoroborate, benzyldimethylphenylammonium hexafluorophosphonate, benzyldimethylphenylammonium hexafluoroarsenate, benzyldimethylphenylammonium trifluoromethane Sulfonate, benzyldimethylphenylammonium trifluoroacetate, benzyldimethylphenylammonium-p-toluenesulfonate, benzyldimethylphenylammonium butyl tris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyl tris (p-chlorophenyl) borate , Benzyl Methylphenylammonium hexyl tris (3-trifluoromethylphenyl) borate, N-cinnamylideneethylphenylammonium tetrafluoroborate, N-cinnamylideneethylphenylammonium hexafluorophosphonate, N-cinnamylideneethylphenylammonium hexafluoroarce Nate, N-cinnamylidene ethylphenylammonium trifluoromethanesulfonate, N-cinnamylideneethylphenylammonium trifluoroacetate, N-cinnamylideneethylphenylammonium-p-toluenesulfonate, N-cinnamylideneethylphenylammonium Butyl tris (2,6-difluorophenyl) borate,
N-cinnamylidene ethyl phenyl ammonium hexyl tris (p-chlorophenyl) borate, N-cinnamylidene ethyl phenyl ammonium hexyl tris (3-trifluoromethylphenyl) borate, etc. are mentioned.

Examples of the sulfonic acid esters include α-hydroxymethylbenzoin-p-toluenesulfonic acid ester, α-hydroxymethylbenzoin-trifluoromethanesulfonic acid ester, α-hydroxymethylbenzoin-methanesulfonic acid ester, pyrogallol- Tri (p-toluenesulfonic acid) ester, pyrogallol-tri (trifluoromethanesulfonic acid) ester, pyrogallol-trimethanesulfonic acid ester, 2,4-dinitrobenzyl-p-toluenesulfonic acid ester, 2,4-dinitrobenzyl- Trifluoromethanesulfonic acid ester, 2,4-dinitrobenzyl-methanesulfonic acid ester, 2,4-dinitrobenzyl-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,6-dini Robenzyl-p-toluenesulfonic acid ester, 2,6-dinitrobenzyl-trifluoromethanesulfonic acid ester, 2,6-dinitrobenzyl-methanesulfonic acid ester, 2,6-dinitrobenzyl-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2-nitrobenzyl-p-toluenesulfonic acid ester, 2-nitrobenzyl-trifluoromethanesulfonic acid ester, 2-nitrobenzyl-methanesulfonic acid ester, 2-nitrobenzyl-1,2-naphthoquinonediazide-5 -Sulfonic acid ester, 4-nitrobenzyl-p-toluenesulfonic acid ester, 4-nitrobenzyl-trifluoromethanesulfonic acid ester, 4-nitrobenzyl-methanesulfonic acid ester,
4-nitrobenzyl-1,2-naphthoquinonediazide-
5-sulfonic acid ester, N-hydroxynaphthalimide-p-toluenesulfonic acid ester, N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester, N-hydroxynaphthalimide-methanesulfonic acid ester, N-hydroxy-5-norbornene- A few
-Dicarboximide-p-toluenesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide-trifluoromethanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide- Methanesulfonic acid ester, 2,4
6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl)
Examples thereof include ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester.

Among these compounds, trichloromethyl-s-triazines include 2- (3-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl)-. 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6- Bis (trichloromethyl)-
s-triazine, 2- [2- (5-methylfuran-2-
Ile) ethenyl] -4,6-bis (trichloromethyl)
-S-triazine, 2- [2- (4-diethylamino-
2-Methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine or 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl)-
s-triazine;

Examples of the diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate and 4
-Methoxyphenylphenyliodonium trifluoromethanesulfonate or 4-methoxyphenylphenyliodonium trifluoroacetate;

As the triarylsulfonium salts,
Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate or 4- Phenylthiophenyldiphenylsulfonium trifluoroacetate;

As the quaternary ammonium salt, tetramethylammonium butyl tris (2,6-difluorophenyl) borate, tetramethylammonium hexyl tris (p-chlorophenyl) borate, tetramethylammonium hexyl tris (3-trifluoromethylphenyl) Borate, benzyl dimethyl phenyl ammonium butyl tris (2,6-difluorophenyl) borate, benzyl dimethyl phenyl ammonium hexyl tris (p-chlorophenyl) borate, benzyl dimethyl phenyl ammonium hexyl tris (3-trifluoromethyl phenyl) borate;

As the sulfonic acid esters, 2,6-
Dinitrobenzyl-p-toluenesulfonic acid ester,
Preferable examples are 2,6-dinitrobenzyl-trifluoromethanesulfonic acid ester, N-hydroxynaphthalimide-p-toluenesulfonic acid ester and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester.

Examples of the radiation-sensitive base generator are disclosed in JP-A-4-330444, "Polymer" p242-24.
8, 46, 6 (1997), US Pat. No. 5,62.
Those described in Japanese Patent Publication No. 7,010 are preferably used. However, the function is not limited to these as long as a base is generated by irradiation with radiation.

Preferred radiation-sensitive base generators in the present invention include photoactive carbamates such as triphenylmethanol, benzylcarbamate and benzoincarbamate; O-carbamoylhydroxylamide, O-carbamoyloxime, aromatic sulfonamide, alpha- Amides such as lactam and N- (2-allylethynyl) amide and other amides;
Examples include oxime ester, α-aminoacetophenone, cobalt complex and the like.

Examples of the radiation-sensitive base generator include compounds represented by the following formulas (19) to (29).

[0158]

[Chemical 40]

(Wherein R ⁷⁶ is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a piperidyl group, A nitro group, a hydroxy group, a mercapto group, an aryl group, a fluorine atom, a chlorine atom or a bromine atom, k is an integer of 0 to 3, R ⁷⁷ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group. And R ⁷⁸
And R ⁷⁹ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ⁷⁸ and R ⁷⁹ are bonded to each other to form a nitrogen atom to which they are bonded. To form a cyclic structure having 5 to 6 carbon atoms. )

[0160]

[Chemical 41]

(Where R⁸⁰Is alkyl having 1 to 6 carbon atoms
Group, alkoxy group having 1 to 6 carbon atoms, thio group having 1 to 6 carbon atoms
Alkyl group, dialkylamino group having 1 to 6 carbon atoms, pipet
Lysyl group, nitro group, hydroxy group, mercapto group or
Is an aryl group, R⁸¹Is a hydrogen atom, having 1 to 6 carbon atoms
An alkyl or aryl group and R⁸²And R
⁸³Are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Group, aryl group, benzyl group or R
⁸²And R⁸³Are the nitrogen sources that are bound to each other and they are bound
Even if it forms a cyclic structure having 5 to 6 carbon atoms with a child
Good. )

[0162]

[Chemical 42]

(Wherein R ⁸⁴ is an alkyl group having 1 to 6 carbon atoms or an aryl group, and R ⁸⁵ and R ⁸⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group. Or R ⁸⁵ and R ⁸⁶ may be bonded to each other to form a cyclic structure having 5 to 6 carbon atoms together with the nitrogen atom to which they are bonded.

[0164]

[Chemical 43]

(Here, R ⁸⁷ and R ⁸⁸ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group.)

[0166]

[Chemical 44]

(Here, R ⁸⁹ , R ⁹⁰ and R ⁹¹ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group.)

[0168]

[Chemical formula 45]

(Wherein R ⁹² is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a piperidyl group, A nitro group, a hydroxy group, a mercapto group or an aryl group, R ⁹³ is a hydrogen atom, an alkyl group or an aryl group having 1 to 6 carbon atoms, and R ⁹⁴ , R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or a carbon atom. It is an alkyl group, an aryl group or a benzyl group of the numbers 1 to 6.)

[0170]

[Chemical formula 46]

(Wherein R ⁹⁷ is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a piperidyl group, A nitro group, a hydroxy group, a mercapto group or an aryl group, and R ⁹⁸ and R ⁹⁹ each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, a cyano group, a phenoxy group, an alkyl group having 1 to 6 carbon atoms, a fluorine atom or chlorine. An atom, a bromine atom or an aryl group and R ¹⁰⁰ and R ¹⁰¹ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ¹⁰⁰ and R ¹⁰¹ are bonded to each other. They may form a cyclic structure having 5 to 6 carbon atoms together with the nitrogen atom to which they are bonded.)

[0172]

[Chemical 47]

(Wherein R ¹⁰² and R ¹⁰³ are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, and a dialkylamino group having 1 to 6 carbon atoms. A group, a piperidyl group, a nitro group, a hydroxy group, a mercapto group or an aryl group, and R ¹⁰⁴
To R ¹⁰⁷ are each independently a hydrogen atom, a hydroxyl group, a mercapto group, a cyano group, a phenoxy group, an alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an aryl group, and A ⁵ is a monoalkylamine , Piperazine, an aromatic diamine or an aliphatic diamine, which is a divalent atomic group formed by removing two hydrogen atoms bonded to one or two nitrogen atoms. )

[0174]

[Chemical 48]

(Here, R ¹⁰⁸ and R ¹⁰⁹ are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, and a dialkylamino group having 1 to 6 carbon atoms. A group, a piperidyl group, a nitro group, a hydroxy group, a mercapto group or an aryl group, and R ¹¹⁰
And R ¹¹¹ are each independently a hydrogen atom, a hydroxyl group, a mercapto group, a cyano group, a phenoxy group, an alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an aryl group, and R ^{112 to} R ¹¹⁵ are each They are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ¹¹² and R ¹¹³ and R ¹¹⁴ and R ¹¹⁵ are nitrogen atoms bonded to each other. And A6 may form a cyclic structure having 5 to ⁶ carbon atoms, and A6 is an alkylene group having 1 to ⁶ carbon atoms, a cyclohexylene group, a phenylene group or a single bond. )

[0176]

[Chemical 49]

(Here, R ^{116 to} R ¹¹⁸ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and a carbon number of 1 to 1.
A C6 alkyl group, a C1-6 alkenyl group, a C1-6 alkynyl group, a C1-6 alkoxy group or an aryl group. )

[0178]

[Chemical 50]

(Where L is a group consisting of ammonia, pyridine, imidazole, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, propylenediamine, 1,2-cyclohexanediamine, N, N-diethylethylenediamine and diethylenetriamine. At least one ligand selected from, m is an integer of 2 to 6, R ¹¹⁹ is an aryl group, and R ¹²⁰ is an alkyl group having 1 to 18 carbon atoms.)

In all of the above formulas (19) to (29), the alkyl group may be linear, branched or cyclic. The aryl group also includes an alkenyl group such as a vinyl group and a propylenyl group; an alkynyl group such as an acetylenyl group; a phenyl group, a naphthyl group, and an anthracenyl group, and these hydrogen atoms are fluorine atoms,
Chlorine atom, bromine atom, halogenated alkyl group, hydroxyl group,
Carboxyl group, mercapto group, cyano group, nitro group,
Those substituted with an azido group, a dialkylamino group, an alkoxy group or a thioalkyl group are also included.

Of these radiation-sensitive base generators, 2
-Nitrobenzylcyclohexylcarbamate, triphenylmethanol, o-carbamoylhydroxylamide, o-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl ] Hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-
Morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaamminecobalt (II
I) Tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and the like are mentioned as preferable ones.

The above (C) radiation-sensitive decomposing agent is preferably used in an amount of 0.01 parts by weight or more based on 100 parts by weight of the total of (A) decomposable polymer and (B) non-decomposable compound.
It is more preferable to use 0.05 part by weight or more.
When the amount of the component (C) is 0.01 part by weight or less, the sensitivity to irradiation light tends to decrease. The upper limit is preferably 30 parts by weight, more preferably 20 parts by weight.

(D) Stabilizer The stabilizer (D) used in the present invention stabilizes the degradable polymer (A) remaining in the refractive index changing material after irradiation with radiation and stabilizes it against an acid or a base. It has the function of imparting sex. By this stabilizing treatment, the refractive index pattern formed by the method of the present invention causes a change in the refractive index even when used under the condition that light near the wavelength used for changing the refractive index passes through. No deterioration and no deterioration.

Examples of the stabilizer (D) include amino compounds, epoxy compounds, thiirane compounds, oxetane compounds, alkoxymethylated melamine compounds, alkoxymethylated glycoluril compounds, alkoxymethylated benzoguanamine compounds, alkoxymethylated urea compounds. , Isocyanate compounds, cyanate compounds, oxazoline compounds, oxazine compounds and silyl compounds (halogenated silyl compounds, other silyl compounds)
Etc. can be mentioned.

As the above amino compound, ammonia,
Trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, triphenylamine, tribenzylamine, aniline, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,3- Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminoontan, 1,9-diaminononane, 1,10-diamino Decane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,4-
Diaminocyclohexane, 1,3-cyclohexanebis (methylamine), 1,3-propan-2-ol,
2,2 ', 2 "-triaminotriethylamine, 1,4
-Diamino-2,2,3,3-tetrafluoropentane,
1,5-diamino-2,2,3,3,4,4-hexafluoropentane, melamine, benzoguanamine, acetoguanamine, acryloguanamine, paramine, amidole, m-phenylenediamine, p-phenylenediamine, p, p '-Diaminodiphenylmethane, diaminodiphenylsulfone, 1,8-diaminonaphthalene,
3,5-diamino-1,2,4-triazole, 2-chloro-4,6-diamino-S-triazine, 2,6-diaminopyridine, 3,3′-diaminobenzidine, bis (4-aminophenyl) Ether, m-xylylenediamine, p-xylylenediamine, 1,2,4,5-benzenetetramine, 2,4-diamino-1,3,5-triazine, 4,4′-diaminobenzophenone, 3,
3 ', 4,4'-tetraaminobenzophenone, triaminobenzene, 4,4'-thiodianiline, 2,3,3
5,6-tetrabromo-p-xylylenediamine, 2,
3,5,6-tetrachloro-p-xylylenediamine,
Examples thereof include 4,5-methylenedioxy-1,2-phenylenediamine and 2,2'-bis (5-aminopyridyl) sulfide.

Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cycloaliphatic epoxy resin,
Examples of commercially available products include bisphenol A type epoxy compounds and aliphatic polyglycidyl ethers.

The following can be exemplified as these commercially available products. As the bisphenol A type epoxy resin, Epicoat 1001, 1002, 100
3, 1004, 1007, 1009, 101
Nos. 0 and 828 (all manufactured by Yuka Shell Epoxy Co., Ltd.) and the like, as bisphenol F type epoxy resin, Epicoat 807 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like, and as phenol novolac type epoxy resin, Epicoat 152, 154 (above, Yuka Shell Epoxy Co., Ltd.)
Manufactured by Nippon Kayaku Co., Ltd., and cresol novolac type epoxy resins such as EOCN-102, EOCN-103S, E.
OCN-104S, EOCN-1020, EOCN-1
025, EOCN-1027 (Nippon Kayaku Co., Ltd.)
C.), Epicoat 180S75 (produced by Yuka Shell Epoxy Co., Ltd.), and the like as a cycloaliphatic epoxy resin.
Y175, CY177, CY179 (above, CIBA-
GEIGY A. G), ERL-4234, ERL-
4299, ERL-4221, ERL-4206 (above, manufactured by U.C.C.), Shoredyne 509 (manufactured by Showa Denko KK), Araldite CY-182, CY-19.
2, the same CY-184 (above, CIBA-GEIGY
A. G), Epichron 200, 400 (above, manufactured by Dainippon Ink and Chemicals, Inc.), Epicoat 871, 872.
(Above, Yuka Shell Epoxy Co., Ltd.), ED-566
1, ED-5662 (above, manufactured by Celanese Coating Co., Ltd.) and the like, as aliphatic polyglycidyl ether, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Epiol TMP (manufactured by NOF Corporation), etc. Can be mentioned.

In addition to the above, phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, N-glycidyl phthalimide, (nonafluoro-N-
Butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N,
N-diglycidylaniline, 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane and the like can be preferably used as the epoxy compound.

As the above-mentioned thiirane compound, the epoxy group of the above-mentioned epoxy compound can be prepared according to, for example, J. Org. Che
m. , 28, 229 (1963), an ethylene sulfide group substituted can be used.

Examples of the oxetane compound include bis [(3-ethyl-3-oxetanylmethoxy) methyl]
Benzene (trade name "XDO", manufactured by Toagosei Co., Ltd.), bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] methane, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] Ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl-
Phenyl] propane, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] sulfone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-
Phenyl] ketone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] hexafluoropropane, tri [(3-ethyl-3-oxetanylmethoxy)
Methyl] benzene, tetra [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and the like can be mentioned.

The above alkoxymethylated melamine compound,
Alkoxymethylated benzoguanamine compounds, alkoxymethylated glycoluril compounds and alkoxymethylated urea compounds convert methylol groups of methylolated melamine compounds, methylolated benzoguanamine compounds, methylolated glycoluril compounds and methylolated urea compounds to alkoxymethyl groups, respectively. It is obtained by doing. The kind of the alkoxymethyl group is not particularly limited, and may be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like.

Examples of commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272 and 202. 1156 and 115
8, 1123, 1170, 1174, UFR6
5, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.),
Nikarac Mx-750, Mx-032, Mx-7
06, the same Mx-708, the same Mx-40, the same Mx-31,
The same Ms-11, Mw-30 (above, Sanwa Chemical Co., Ltd. make) etc. can be mentioned.

Examples of the above-mentioned isocyanate compound include phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate and 1-methylphenylene-
2,4-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3
-Xylylene diisocyanate, 1,4-xylylene diisocyanate, biphenylene-4,4'-diisocyanate, 3,3'-dimethoxybiphenylene-4,4 '
-Diisocyanate, 3,3'-dimethylbiphenylene-4,4'-diisocyanate, diphenylmethane-
2,4'-diisocyanate, diphenylmethane-4,
4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 3,3'-
Dimethyldiphenylmethane-4,4'-diisocyanate, naphthylene-1,5-diisocyanate, cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,
3-diisocyanate, cyclohexylene-1,4-diisocyanate, 1-methylcyclohexylene-2,4
-Diisocyanate, 1-methylcyclohexylene-
2,6-diisocyanate, 1-isocyanate-3,
3,5-Trimethyl-5-isocyanate methylcyclohexane, cyclohexane-1,3-bis (methylisocyanate), cyclohexane-1,4-bis (methylisocyanate), isophorone diisocyanate, dicyclohexylmethane-2,4′-diisocyanate, dicyclohexyl Methane-4,4'-diisocyanate,
Ethylene diisocyanate, tetramethylene-1,4-
By reacting diisocyanate, hexamethylene-1,6-diisocyanate, dodecamethylene-1,12-diisocyanate, lysine diisocyanate methyl ester, etc., and a stoichiometric excess of these organic diisocyanates with a bifunctional active hydrogen-containing compound. Examples thereof include the isocyanate-terminated prepolymers obtained at both ends.

In addition to the above diisocyanate, for example, phenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, diphenylmethane-2,5,4'-triisocyanate and triphenylmethane. -2,4 ', 4 "-triisocyanate, triphenylmethane-4,4', 4"
-Triisocyanate, diphenylmethane-2,4
2 ', 4'-tetraisocyanate, diphenylmethane-2,5,2', 5'-tetraisocyanate, cyclohexane-1,3,5-triisocyanate, cyclohexane-1,3,5-tris (methylisocyanate), 3 , 5-Dimethylcyclohexane-1,3,5-
Tris (methylisocyanate), 1,3,5-trimethylcyclohexane-1,3,5-tris (methylisocyanate), dicyclohexylmethane-2,4,2 ′
-Triisocyanate, dicyclohexylmethane-2,
Trifunctional or more trifunctional organic polyisocyanates such as 4,4′-triisocyanate, or a stoichiometric excess of these trifunctional or more polyfunctional polyisocyanates with a difunctional or more polyfunctional active hydrogen-containing compound You may use together the obtained terminal isocyanate prepolymer etc.

The above cyanate compounds include 1,3-
Dicyanate benzene, 1,4-dicyanate benzene, 1,3,5-tricyanate benzene, 1,3-,
1,4-, 1,6-, 1.8-, 2.6-, or 2,
7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 2,2′- or 4,4′-dicyanatobiphenyl, bis (4-cyanatophenyl) methane, 2,2-bis (4 -Cyanatophenyl) propane, 2,2'-bis (3,5-dichloro-4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) ethane, bis (4-cyanatophenyl) Ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, 1,
1,1,3,3,3-hexafluoro-2,2-bis (4-cyanatophenyl) propane, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, and phenol Benzene polynuclear polyisocyanate compound obtained by reaction of resin and cyanogen halide (for example, JP-B-45-11)
712 and 55-9433). A divalent cyanate ester derived from a bisphenol such as 2,2-bis (4-cyanatophenyl) propane from the viewpoints of being easily available and imparting good properties to the moldability and the final cured product. The compounds are used particularly well. Further, a polycyanate obtained by reacting an initial condensate of phenol and formaldehyde with cyanogen halide is also useful.

As the above-mentioned oxazoline compound, 2,
2'-bis (2-oxazoline), 4-furan-2-ylmethylene-2-phenyl-4H-oxazole-5-
On, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2)
-Oxazolyl) benzene, 2,3-bis (4-isopropenyl-2-oxazolin-2-yl) butane, 2,
2'-bis-4-benzyl-2-oxazoline, 2,6
-Bis (isopropyl-2-oxazolin-2-yl)
Pyridine, 2,2'-isopropylidene bis (4-te
rt-butyl-2-oxazoline), 2,2′-isopropylidene bis (4-phenyl-2-oxazoline),
2,2'-methylenebis (4-tert-butyl-2-
Oxazoline), 2,2'-methylenebis (4-phenyl-2-oxazoline) and the like.

Examples of the oxazine compound include 2,2 '
-Bis (2-oxazine), 4-furan-2-ylmethylene-2-phenyl-4H-oxazyl-5-one,
1,4-bis (4,5-dihydro-2-oxazyl) benzene, 1,3-bis (4,5-dihydro-2-oxazyl) benzene, 2,3-bis (4-isopropenyl-
2-oxazin-2-yl) butane, 2,2′-bis-
4-benzyl-2-oxazine, 2,6-bis (isopropyl-2-oxazin-2-yl) pyridine, 2,
2'-isopropylidene bis (4-tert-butyl-
2-oxazine), 2,2'-isopropylidenebis (4-phenyl-2-oxazine), 2,2'-methylenebis (4-tert-butyl-2-oxazine),
2,2'-methylenebis (4-phenyl-2-oxazine) and the like can be mentioned.

Examples of the silyl halide compound include tetrahalosilanes such as tetrachlorosilane, tetrabromosilane, tetraiodosilane, trichlorobromosilane, dichlorodibromosilane, methyltrichlorosilane, methyldichlorobromosilane, cyclohexyltrichlorosilane and the like. Monoalkyltrihalogenosilanes, phenyltrichlorosilane, naphthyltrichlorosilane, 4-chlorophenyltrichlorosilane, phenyldichlorobromosilane and other monoaryltrihalogenosilanes, phenoxytrichlorosilane, phenoxydichlorobromosilane and other monoaryloxytrihalogenosilanes , Methoxytrichlorosilane, ethoxytrichlorosilane and other monoalkoxytrihalogenosilanes,
Dialkyldihalogenosilanes such as dimethyldichlorosilane, methyl (ethyl) dichlorosilane, methyl (cyclohexyl) dichlorosilane, monoalkylmonoaryldihalogenosilanes such as methyl (phenyl) dichlorosilane, diaryldihalogenosilanes such as diphenyldichlorosilane Silanes, diaryloxydihalogenosilanes such as diphenoxydichlorosilane, monoalkylmonoaryloxydihalogenosilanes such as methyl (phenoxy) dichlorosilane, monoarylmonoaryloxydihalogenosilanes such as phenyl (phenoxy) dichlorosilane , Dialkoxydihalogenosilanes such as diethoxydichlorosilane, monoalkyl monoalkoxydichlorosilanes such as methyl (ethoxy) dichlorosilane, phenyl ) Monoarylmonoethoxydichlorosilanes such as dichlorosilane, trialkylmonohalogenosilanes such as trimethylchlorosilane, dimethyl (ethyl) chlorosilane, dimethyl (cyclohexyl) chlorosilane, dialkylmonoarylmonohalogenosilanes such as dimethyl (phenyl) chlorosilane , Monoalkyldiarylmonohalogenosilanes such as methyl (diphenyl) chlorosilane, triaryloxymonohalogenosilanes such as triphenoxychlorosilane, monoalkyldiaryloxymonohalogenosilanes such as methyl (diphenoxy) chlorosilane, phenyl (diphenoxy) chlorosilane And other monoaryldiaryloxymonohalogenosilanes, and dimethyl (phenoxy) chlorosilane and other dialkylmonoaryl groups Simonohalogenosilanes, diarylmonoaryloxymonohalogenosilanes such as diphenyl (phenoxy) chlorosilane, monoalkylmonoarylmonoaryloxymonohalogenosilanes such as methyl (phenyl) (phenoxy) chlorosilane, triethoxy such as triethoxychlorosilane Examples thereof include oligomers of the above compounds such as monohalogenosilanes and tetrachlorosilane dimers and pentamers.

Examples of the other silyl compounds include hexamethyldisilazane, t-butyldimethylchlorosilane, bis (trimethylsilyl) trifluoroacetamide, diethylaminotrimethylsilane, trimethylsilanol, hexamethyldisiloxane, chloromethyldimethylethoxysilane, and acetyltrisilane. Phenylsilane, ethoxytriphenylsilane, triphenylsilanol,
Triethylsilanol, tripropylsilanol, tributylsilanol, hexaethyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxylane, acetoxyethyldimethylchlorosilane, 1,3-bis (hydroxybutyl) tetramethyldisiloxane, 1,3-
Bis (hydroxypropyl) tetramethyldisiloxane, γ-aminopropylmethoxysilane, γ-aminopropylethoxysilane, N-β (aminoethyl) -γ-
Aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane,
N-phenyl-γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-dibutylaminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-β (N-vinylbenzylaminoethyl)- γ-aminopropyltrimethoxysilane ・ hydrochloride, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) Silane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysila , .Gamma.-mercaptopropyltrimethoxysilane, .gamma.-chloropropyl trimethoxy silane, trimethylchlorosilane, hexamethyldisilazane, N- trimethylsilyl imidazole, bis (trimethylsilyl) urea, trimethylsilylacetamide, bistrimethylsilylacetamide, trimethylsilylisocyanate, trimethylmethoxysilane,
Trimethylethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, t-butyldimethylchlorosilane, t-butyldiphenylchlorosilane, triisopropylchlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane. , N-hexyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, dimethylsilyldiisocyanate, methylsilyltriisocyanate, phenyltrimethoxysilane, diphenyl Examples thereof include dimethoxysilane, phenylsilyltriisocyanate and the like.

As the stabilizer (D) used in the present invention, among the above, an amino compound, an epoxy compound, a thiirane compound, an oxetane compound, an oxazoline compound,
Oxazine compounds, silyl compounds, isocyanate compounds and cyanate compounds are preferred, and among these, amino compounds, epoxy compounds, thiirane compounds, oxetane compounds, oxazoline compounds and oxazine compounds are more preferred. Among them, particularly, ethylenediamine, phenylglycidyl ether, 3-phenoxypropylene sulfide, 3,3,3-trifluoropropylene oxide, hexamethyldisilazane, γ-
Aminopropylmethoxysilane, γ-glycidoxypropyltrimethoxysilane, methylsilyltriisocyanate and the like are preferably used.

These (D) stabilizers can be used alone or in combination of two or more kinds. The component (D) can be used in an excess amount so that the remaining portion of the decomposable compound (A) can be sufficiently reacted.
10 parts by weight or more per 100 parts by weight of the component (A),
Preferably 30 parts by weight or more can be used.
When the amount of the component (D) is less than 10 parts by weight, the reaction may be insufficient and the stability of the refractive index changing material may be insufficient.

A catalyst may be used together with the stabilizer (D). The use of the catalyst promotes the reaction between the component (D) and the remaining part of the decomposable compound (A).

Examples of such a catalyst include acid catalysts,
Examples thereof include base catalysts and quaternary onium salts.

Examples of the above acid catalyst include organic acids such as acetic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid and trifluoromethanesulfonic acid, hydrochloric acid,
Inorganic acids such as sulfuric acid and nitric acid, as the base catalyst,
Alkali metal carbonates such as sodium carbonate, potassium carbonate or lithium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate or lithium hydrogen carbonate; alkali metal acetates such as sodium acetate; lithium hydride, Alkali metal hydrides such as sodium hydride or potassium hydride; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide or lithium hydroxide; sodium methoxide,
Alkali metal alkoxides such as sodium ethoxide, potassium t-butoxide or lithium methoxide; mercaptan alkali metals such as methyl mercaptan sodium or ethyl mercaptan sodium; triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, pyridine,
4- (N, N-dimethylamino) pyridine, N, N-dimethylaniline, N, N-diethylaniline, 1,5-
Diazabicyclo [4.3.0] non-5-ene, 1,4
-Diazabicyclo [2.2.2] octane (DABC
O) or organic amines such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU); alkyl lithiums such as methyl lithium, ethyl lithium or butyl lithium; lithium diisopropylamide or lithium. Further, lithium alkylamides such as dicyclohexylamide, and the like, as the quaternary onium salts, for example, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodo, tetrabutylammonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium. Bromide, cetyltrimethylammonium bromide, tetrapropylammonium bromide, benzyltriethylammonium chloride, etc. That. Also, 18-crown-6-
It is also possible to use ether as a catalyst in combination with salts such as potassium chloride, potassium bromide, potassium iodide, cesium chloride, potassium phenoxide, sodium phenoxide and potassium benzoate.

Of these, preferred catalysts are p-
Toluene sulfonic acid, hydrochloric acid, sulfuric acid, sodium hydroxide,
Potassium t-butoxide, triethylamine, DBU,
Mention may be made of tetrabutylammonium bromide, tetrabutylphosphonium bromide, 18-crown-6-ether / potassium phenoxide.

The amount of these catalysts used is such that the component (D) is an amino compound, an alkoxymethylated melamine compound,
When using an alkoxymethylated glycoluril compound, an alkoxymethylated benzoguanamine compound, an alkoxymethylated urea compound, and a silyl halide compound, the amount used is preferably 2 mol or less per 1 equivalent of the component (D).

Further, as the component (D), an epoxy compound,
When a thiirane compound, an oxetane compound, an isocyanate compound, a cyanate compound, an oxazoline compound, an oxazine compound, or another silyl compound is used,
The amount used is preferably 0.2 mol or less per 1 equivalent of the component (D).

Here, the number of equivalents used of the component (D) is
It is a value obtained by multiplying the amount (mol) of the component (D) used by the number of reactive groups contained in the component (D). The number of reactive groups depends on the type of the component (D). Is defined as

In the case of amino compounds; in the number of nitrogen atoms; in the case of epoxy compounds; in the number of epoxy groups; in the case of thiirane compounds; in the case of oxetane compounds; in the number of oxetanyl groups; in the number of alkoxymethylated melamine compounds; Uryl compounds, alkoxymethylated benzoguanamine compounds and alkoxymethylated urea compounds; number of alkoxymethyl groups; isocyanate compounds; number of isocyanate groups; cyanate compounds; number of cyanate groups; oxazoline compounds; number of oxazolyl groups oxazine In the case of compounds: Number of oxazyl groups Halogenated silyl compounds; Number of halogen atoms bonded to silicon atoms Other silyl compounds; Number of silicon atoms

<Other Components> The refractive index changing composition used in the present invention may contain other additives as long as the object of the present invention is not impaired. Examples of such additives include an ultraviolet absorber, a sensitizer, a surfactant, a heat resistance improver, and an adhesion aid.

Examples of the UV absorber include UV absorbers such as benzotriazoles, salicylates, benzophenones, substituted acrylonitriles, xanthenes, coumarins, flavones and chalcones. Specifically, TINUVIN 234 (2- (2-hydroxy-) manufactured by Ciba Specialty Chemicals Co., Ltd.
3,5-bis (α, α-dimethylbenzyl) phenyl)
-2H-benzotriazol), tinuvin 571 (hydroxyphenylbenzotriazol derivative), tinuvin 1130 (methyl-3- (3-t-butyl-5- (2H
-Benzotriazol-2-yl) -4-hydroxyphenyl) propionate-polyethylene glycol (condensation product with molecular weight 300)), 1,7-bis (4-hydroxy-3-methoxyphenyl) -1 , 6-heptadiene-3,5-dione, dibenzylideneacetone and the like.

By adding an ultraviolet absorber, the amount of acid or base generated from the component (C) is gradually decreased as the depth of the irradiated portion of the refractive index changing composition of the present invention from the surface becomes deeper. And is useful as a GRIN forming means. The proportion of these ultraviolet absorbers used is preferably 30 parts by weight or less, more preferably 20 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).
It is less than or equal to parts by weight.

Examples of the sensitizer include coumarins having a substituent at the 3-position and / or the 7-position, flavones, dibenzalacetones, dibenzalcyclohexanes, chalcones, xanthenes and thiols. Xanthenes, porphyrins, phthalocyanines, acridines, anthracenes and the like can be used.

The ratio of the sensitizer used is that of the components (A) and (B).
It is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the total of the components.

Further, the above-mentioned surfactant can be added in order to improve the coatability, for example, to prevent striation and to improve the developability.

Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and the like. Polyoxyethylene aryl ethers, polyethylene glycol dilaurate,
Nonionic surfactants such as polyethylene glycol dialkyl esters such as polyethylene glycol distearate; Ftop EF301, EF303, E
F352 (above, manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F172, F173 (above manufactured by Dainippon Ink and Chemicals), Florard FC430, FC43
1 (above, Sumitomo 3M Limited), Asahi Guard A
G710, Surflon S-382, SC-101, SC
-102, SC-103, SC-104, SC-10
5, SC-106 (above, manufactured by Asahi Glass Co., Ltd.) and other commercially available fluorine-based surfactants; organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (Co) Polymer Polyflow No. Other surfactants marketed under the trade name of 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) can be used.

The use ratio of these surfactants is (A)
It is preferably 2 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the total amount of the component and the component (B).

Further, the above-mentioned adhesion aid can be added to improve the adhesion to the substrate, and a silane coupling agent or the like is preferably used.

As the heat resistance improver, an unsaturated compound such as a polyvalent acrylate can be added.

Further, in the refractive index changing material used in the present invention, if necessary, an antistatic agent, a storage stabilizer,
An antihalation agent, an antifoaming agent, a pigment, a thermal acid generator, etc. can also be added.

<Formation of Refractive Index Pattern> In the present invention, the refractive index pattern can be formed, for example, as follows by using the above-mentioned refractive index changing composition.

First, the refractive index changing composition is dissolved or dispersed in a solvent so that the concentration of its solid content is 5 to 70% by weight to prepare a composition. Pore size 0.
You may use it, after filtering with a filter of about 1-10 μm.

Thereafter, the composition is applied to the surface of a substrate such as a silicon wafer and prebaked to remove the solvent, thereby forming a coating film of the refractive index changing composition. Next, the formed coating film is subjected to radiation irradiation treatment, for example, through a pattern mask, and then a portion of the coating film is subjected to radiation treatment, so that the radiation-irradiated portion and the radiation-unirradiated portion of the refractive index changing composition are treated. A refractive index difference of is formed.

Upon irradiation with radiation, an acid or base is produced from the radiation-sensitive decomposing agent of component (C), and this acid or base acts on component (A) to decompose component (A). This decomposed product mainly escapes during heating after irradiation with radiation. As a result, a difference in refractive index occurs between the radiation-irradiated portion and the radiation-unirradiated portion.

Further, during the heating, the components (A) and (D) remaining without reacting with the acid or base react to stabilize the formed refractive index pattern.

As the solvent for preparing the solution containing the refractive index changing composition used in the present invention, the above-mentioned (A), (B), (C), (D) and optionally added. A substance that uniformly dissolves each component of other additives and does not react with each component is used.

Specifically, for example, alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, ethylene glycol and propylene glycol; ethers such as tetrahydrofuran;
Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether Diethylene glycols; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether Propylene glycol alkyl ether acetates such as teracetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether pro Propylene glycol alkyl ether acetates such as pionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;

And methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate,
Ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate,
Butyl lactate, methyl 3-hydroxypropionate, 3-
Ethyl hydroxypropionate, Protyl 3-hydroxypropionate, Butyl 3-hydroxypropionate,
Methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butylacetate, methyl propoxyacetate, ethyl propoxyacetate,
Propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxypropionic acid Butyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate , Butyl 2-butoxypropionate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Propyl 3-methoxypropionate, Butyl 3-methoxypropionate, 3-Ethoxypropionate Methyl acidate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxypropione Butyl acid ester, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like;

Trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene, hexafluorobenzene, hexafluorocyclohexane, perfluorodimethylcyclohexane, perfluoromethylcyclohexane, octafluorodecalin, 1,1,2-trichloro-1, A solvent containing a fluorine atom such as 2,2-trifluoroethane may be mentioned.

Among these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates are used because of their solubility, reactivity with each component, and ease of forming a coating film. , Ketones, esters and diethylene glycols are preferably used.

Further, a high boiling point solvent may be used in combination with the above solvent. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether. , Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol,
1-nonanol, benzyl alcohol, benzyl acetate,
Examples thereof include ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and phenyl cellosolve acetate.

The refractive index changeable composition used in the present invention is molded into various shapes in consideration of the application when it is irradiated with radiation. For example, rod shape, fiber shape,
Examples include, but are not limited to, a long plate shape, a spherical shape, a film shape, and a lens shape. As the molding method, a method usually used can be used. For example, injection molding, compression molding, blow molding, extrusion, in-box polymerization method, shaving method, drawing method, heating and cooling method, CVD
A vapor deposition method, a sintering method, a scanning method and the like can be mentioned. Further, depending on the use of the optical molded article, a spin coating method, a slit method, a bar coating method, a solvent casting method, an LB method, a spray method, a roll coating method, a relief printing method, a screen printing method or the like can be used.

In this molding treatment, a heat treatment (hereinafter,
It is called "prebaking". ) Is preferable. The heating condition varies depending on the composition of the material of the present invention, the type of each additive, etc., but is preferably 30 to 200 ° C., more preferably 40 to 150 ° C., using a hot plate, oven, infrared ray, or the like. Can be heated.

As radiation used for radiation treatment
Is an i-line with a wavelength of 365 nm, an h-line with a wavelength of 404 nm, 436
nm g-line, ultraviolet of wide-wavelength light source such as xenon lamp
Line, 248 nm wavelength KrF excimer laser, wavelength 1
Far-ultraviolet rays such as 93 nm ArF excimer laser
Charged particles such as X-rays such as crotron radiation or electron beams
Lines, visible light and mixed lines of these, and the like. this
Of these, ultraviolet light and visible light are preferred. As illuminance
Is 0.1 mW / cm, depending on the irradiation wavelength ²-10
0 mW / cm²Is the most efficient reaction and is preferable.
Yes. These radiations are emitted through the pattern mask.
Patterning the radiation-sensitive refractive index changing material by
It is possible to Used as patterning accuracy
Depending on the light source, etc., a solution of about 0.2 μm
It is possible to manufacture optical parts with refractive index change distribution with image
It

In the present invention, it is preferable to carry out a heat treatment (post-irradiation baking (PEB)) after the exposure. An apparatus similar to the above prebaking can be used for the heating, and the conditions can be set arbitrarily. The preferred heating temperature is 30 to 150 ° C, more preferably 30 to 130 ° C.
Is. In addition, it is preferable to carry out a heat treatment for stabilizing the remaining components (A) and (D) by reaction either continuously or separately from the baking after irradiation with radiation. The heat treatment for stabilization is preferably 35 to 200 ° C, more preferably 10 ° C or more higher than the temperature of PEB,
More preferably, the temperature is 20 ° C. or more higher than the temperature of PEB.

Further, it remains in the unirradiated portion (C).
A re-exposure treatment can be performed in order to decompose the components and the like and further improve the stability of the material.

The re-exposure process can be carried out, for example, by irradiating the entire surface of the pattern with a radiation having a similar wavelength as the radiation used in the step of changing the refractive index.

If desired, the stability of the material can be further increased by further performing heat treatment. For heating at this time, an apparatus similar to the prebaking at the time of material molding can be used, and the conditions can be set arbitrarily.

Further, according to the present invention, the method for forming a refractive index pattern of the present invention comprises: It can also be carried out by irradiating with radiation and then treating with (D) a stabilizer.

The treatment with the stabilizer (D) is preferably carried out after the post-exposure bake.

The stabilizer (D) has a function of stabilizing the decomposable compound (A) remaining in the refractive index changing material after irradiation with radiation and imparting stability to an acid or a base. By this stabilizing treatment, the refractive index pattern formed by the method of the present invention causes a change in the refractive index even when used under the condition that light near the wavelength used for changing the refractive index passes through. No deterioration and no deterioration.

As the stabilizer (D), a low boiling point compound such as ammonia or triethylamine can be used in addition to the above-mentioned specific examples.

Any appropriate method can be adopted for contacting the refractive index changing composition after irradiation with radiation and the stabilizer (D) in the stabilization treatment. For example, the component (D) and, depending on the case, a catalyst is suitable. It can be dissolved in a solvent and brought into contact with the refractive index changing composition in a solution state, or (D) component 100 when (D) component is a liquid or gas under the contact conditions.
It is also possible to directly contact in the state of%.

When a solvent is used in the reaction between the stabilizer (D) and the component (A), the solvent dissolves the component (D) and the optionally added catalyst, but does not dissolve the component (A). Those are preferable. By selecting such a solvent, the surface of the obtained refractive index pattern is not roughened.

Examples of such a solvent include water; methanol, ethanol, iso-propanol, n-propanol, n-butanol, iso-butanol, te.
Alcohols such as rt-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol; ethers such as diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methyl cellosolve acetate, ethyl cellosolve Ethylene glycol alkyl ether acetates such as acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether and propylene glycol ethyl ether; Propylene glycol methyl ether Propylene glycol alkyl ether acetates such as teracetate and propylene glycol ethyl ether acetate; propylene such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate Glycol alkyl ether acetates; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane; methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl amyl ketone, 4- Ketones such as hydroxy-4-methyl-2-pentanone; and ethyl acetate,
Propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, butyl hydroxyacetate,
Ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, ethyl methoxyacetate, butyl methoxyacetate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, 2- Butyl ethoxypropionate,
Butyl 2-butoxypropionate, Butyl 3-methoxypropionate, Butyl 3-ethoxypropionate, 3-
Esters such as butyl propoxypropionate and butyl 3-butoxypropionate; trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene,
Hexafluorobenzene, hexafluorocyclohexane, perfluorodimethylcyclohexane, perfluoromethylcyclohexane, octafluorodecalin,
Fluorine atom-containing solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane may be mentioned.

Among these solvents, water, alcohols,
Glycol ethers, ethylene glycol alkyl ether acetates, and fluorine atom-containing solvents are preferably used.

The reaction temperature for carrying out the reaction of (D) the stabilizer and (A) the remaining portion of the decomposable compound can be usually 0 to 130 ° C., and the reaction time is usually 10 seconds to 1 hour. can do.

Further, it remains in the unirradiated portion (C).
A re-exposure treatment can be performed in order to decompose the components and the like and further improve the stability of the material.

It should be noted that if there is no description about the refractive index pattern forming method including the above-mentioned stabilization treatment, the matters described about the above-mentioned refractive index pattern forming method may be applied as they are or under changes obvious to those skilled in the art. Should be understood.

Further, according to the present invention, the method for forming a refractive index pattern of the present invention is characterized in that a refractive index changing composition comprising the above-mentioned component (A), component (B) and component (C) is exposed to radiation through a pattern. Of the unexposed part (A)
It can also be carried out by decomposing a decomposable compound.

The above heating is preferably carried out at a temperature higher than the temperature of baking after irradiation by 10 ° C. or more. For example, a temperature of 170 ° C. or higher is preferable, and a temperature of 200 ° C. or higher is more preferable.

By the above heating, the decomposable compound (A) remaining in the unexposed area is removed by decomposition or sublimation, and preferably, voids are not substantially formed.

Regarding the matters not described in the above refractive index pattern forming method in the case where the component (D) is not contained, the matters related to the above-mentioned pattern forming method are as they are or are obvious to those skilled in the art. It should be understood that it applies under modification.

In the refractive index pattern of the present invention formed by various methods as described above, the refractive index of the radiation-irradiated portion (first region) is preferably the refractive index of the unirradiated portion (second region). Less than the rate. This difference can be arbitrarily adjusted by adjusting the types and contents of the components (A) and (B) in the refractive index changing composition used in the present invention. For example, the maximum value of the refractive index difference is 0. It can be a value greater than 0.02.

The refractive index pattern of the present invention has or does not have a void in the radiation irradiated portion.

When the radiation-irradiated portion has voids, the void ratio is preferably 10 to 99.9%, more preferably 15 to 99.9%, and particularly preferably 20 to 9%.
It is 9.9%.

Furthermore, the elastic modulus of the radiation-irradiated portion and the non-irradiated portion are preferably 0.3 GPa or more and 1 respectively.
GPa or more, more preferably 0.5 G each
Pa or higher and 3 GPa or higher.

The elastic modulus of the radiation-irradiated portion is preferably smaller than that of the radiation-unirradiated portion.

Further, the refractive index pattern of the present invention may cause a change in the refractive index even when used under the condition that light near the wavelength used for changing the refractive index passes as described above. Since it does not deteriorate and does not deteriorate, it is extremely useful as an optical material used in the fields of optoelectronics and displays.

The refractive index pattern of the present invention has a sufficiently large refractive index difference, and since the formed refractive index difference is stable to light and heat, it is used in the fields of optoelectronics and displays. It is extremely useful as an optical material. The refractive index pattern of the present invention includes other photo arrays, various lenses, photo couplers, photo interrupters,
Polarization beam splitter, hologram, single mode /
Multimode optical fiber, bundle fiber, various light guides, optical connector such as single core / multicore / photoelectric coupling, optical isolator, polarizer, photodiode / phototransistor / photo IC / CCD image sensor / CMO
S image sensor / optical fiber sensor, optical sensor such as optical fiber gyro, optical disk such as CD / LD / PD / DVD, optical switch, waveguide, optical touch panel, diffraction grating, light guide plate, light diffusion plate, antireflection Used for optical components such as plates and optical sealing materials.

<Method for Manufacturing Optical Parts> The photosensitive refractive index changing composition is molded into various shapes in consideration of application when irradiated with light.

For example, rod shape, fiber shape, long plate shape,
Examples thereof include spherical shapes, film shapes, and lens shapes, but are not limited thereto. As the molding method, a commonly used method can be used, for example, injection molding,
Examples include compression molding, blow molding, extrusion, polymerization in a box frame, shaving, stretching, heating and cooling, CVD deposition, sintering, and scanning. Further, depending on the use of the optical molded article, a spin coating method, a slit method, a bar coating method, a solvent casting method, an LB method, a spray method, a roll coating method, a relief printing method, a screen printing method or the like can be used.

The light used for the light irradiation treatment includes i-line with a wavelength of 365 nm, h-line with a wavelength of 404 nm, g-line with a wavelength of 436 nm.
Rays, ultraviolet rays from a wide wavelength light source such as a xenon lamp, a KrF excimer laser with a wavelength of 248 nm, a wavelength of 193 nm
Far-ultraviolet rays such as ArF excimer laser, charged particle beams such as X-rays or electron beams such as synchrotron radiation, visible light, and mixed rays thereof. Of these, ultraviolet light and visible light are preferable. The illuminance is 0.1 mW / cm ^{2 to} 100 mW, depending on the irradiation wavelength.
/ Cm ² is most preferable because the reaction efficiency is highest. By irradiating these radiations through a pattern mask, the radiation-sensitive refractive index changing composition can be patterned. Although the patterning accuracy is affected by the light source used, it is possible to manufacture an optical component having a refractive index change distribution with a resolution of about 0.2 μm.

In the present invention, it is preferable to carry out a heat treatment after exposure (hereinafter referred to as "post-exposure bake"). The heating condition varies depending on the compounding composition of the material of the present invention, the type of each additive, etc., but is preferably 30 to 200.
C., more preferably 40 to 150.degree. C., and can be heated using a hot plate, oven, infrared ray or the like.

The difference between the maximum refractive index and the minimum refractive index in the refractive index distribution of the optical component of the present invention can be set arbitrarily according to the application as described above, but is, for example, 0.02.
It can be set to the above, and it can be set to 0.03 or more, further 0.05 or more, 0.08 or more as required.

Next, as a concrete example, a method for forming an optical fiber, a lens, an optical waveguide, a diffraction grating, a hologram element and a recording medium will be described in detail.

<Method of forming optical fiber> The optical fiber can be formed by an appropriate method.
The following method can be used.

The photosensitive refractive index changing composition for forming an optical fiber can be used in a state of being dissolved in a suitable solvent. As the solvent used at this time, a solvent having a boiling point of 50 ° C to 200 ° C can be used, and the solid content concentration in the solution can be 50% to 80%.
This solution is used as a stock solution of fibers, and after defoaming, a fiber shape is formed by heat drawing, laser irradiation drawing, extrusion or the like. The pore size at this time is 0.1 to 1.0 m
A value of about 0.1 to 1,000 m / min can be adopted as m and the stretching speed.

Next, the fiber formed as described above is uniformly illuminated from the periphery of the fiber toward the center by using a ring-shaped light source such as an optical fiber or a reflection plate, and then a post-exposure bake is performed. By doing so, the optical fiber of the present invention can be formed. The post-exposure bake temperature at this time may be 50 ° C. to 200 ° C., and the baking time may be 1 second to 30 minutes. As a heating heat source, an appropriate heat source such as an infrared lamp can be used.

At this time, adjustment of light irradiation amount, selection of wavelength,
Further, by using the ultraviolet absorber, it is possible to form a GI type optical fiber having a distribution in which the refractive index decreases parabolicly from the central axis to the periphery.

The fiber stretching device, radiation irradiating device and heating device described above can be continuous steps. This makes it possible to continuously manufacture GI type optical fibers and the like.

<Lens Forming Method> The lens of the present invention can be formed by an appropriate method, for example, the following method.

Formation of GRIN lens having concave lens ability
Method The photosensitive refractive index changing composition used for forming a lens can be used in a state of being dissolved in a suitable solvent. The solvent used at this time has a boiling point of 50 ° C to 200 ° C.
Can be used, and the solid content concentration in the solution is 5
It can be 0 to 80%. This solution is formed into a disc having a desired shape by hot pressing or the like. Next, the GRIN lens having a concave lens function is formed by performing light irradiation so that the exposure amount of the central portion of the disc is large and the exposure amount decreases as it goes to the circumferential portion, and then baking is performed after the exposure. can do. As the irradiation device at this time, for example, a device as shown in FIG. 1 can be used. In the irradiation apparatus of FIG. 1, an openable and closable diaphragm 2 is attached in front of a disc-shaped sample 1, and only parallel light from the light source is irradiated while gradually opening the diaphragm 2 from 1 to 5 seconds. The above-mentioned exposure state is realized by adjusting the shutter speed so that the diaphragm 2 is completely opened in a minute. The heating condition for the post-exposure bake is 1 at 50 to 200 ° C.
Seconds to 30 minutes can be adopted.

Formation of GRIN lens having convex lens ability
Method For a disk-shaped sample similar to the one described above, perform post-exposure bake after irradiating light so that the exposure amount at the circumference of the disk is large and the exposure amount becomes smaller toward the center. As a result, a GRIN lens having a convex lens function can be obtained. Such an exposure state can be realized by, for example, shielding the upper and lower portions of the cylinder and allowing the light to uniformly enter only from the side surface. An optical fiber, a reflection plate, or the like can be used for uniform light irradiation from the side surface. For the post-exposure bake, the same conditions as above can be adopted.

<Method of forming optical waveguide> The optical waveguide of the present invention can be formed by an appropriate method, for example, the following method can be used.

The photosensitive refractive index changing composition for forming an optical waveguide can be used in a state of being dissolved in a suitable solvent (solution A). As the solvent used at this time, a solvent having a boiling point of 50 ° C. to 200 ° C. can be used, and the solid content concentration in the solution can be 20 to 60%. Separately from this solution, a composition solution in which a thermal acid generator and / or a photoacid generator is added to the component (B) is prepared (solution B). The solid content concentration in this solution can be 20 to 60%, and a solvent having a boiling point of about 50 ° C to 200 ° C can be used.

First, the solution B is applied onto an appropriate substrate such as silicon or glass, and the solvent is removed to give a thickness of 1
A coating film of about 50 μm is formed. This coating film becomes the lower clad layer. As a coating method at this time, an appropriate method such as a spin coater or a slit coater can be adopted, and the solvent removal condition is 50 ° C. to 150 ° C. for 1 minute to 30 minutes.
It can be heated for about a minute. Next, the solution A is applied onto the lower clad layer formed above, the solvent is removed, and an intermediate layer having a thickness of about 1 to 50 μm is formed. The coating method and solvent removal conditions can be the same as described above.

Next, a photomask in which the waveguide pattern is shielded at the core portion is used to irradiate light, and then post-exposure bake is performed. At this time, the unexposed portion becomes the core portion and the exposed portion becomes the side clad layer. The post-exposure bake conditions are 50 ° C. to 200 ° C. and 1 second to 30 seconds.
It can be about a minute. Then, the solution B is applied again, the solvent is removed, and an upper clad layer having a thickness of about 1 to 50 μm is formed, whereby an optical waveguide can be formed. Since the optical waveguide obtained here contains a thermal acid generator in the upper and lower portions, a slight amount of generated acid is diffused at the interface between the core layer and the upper and lower clad layers. This makes the upper part,
The interface between the core layer and the clad layer can have a structure in which the refractive index gradually changes in both the side portion and the lower portion, and the obtained optical waveguide is a GI type.

<Method of Forming Recording Medium> The recording medium of the present invention can be formed by an appropriate method. For example, the following method can be used.

The photosensitive refractive index changing composition for forming a recording medium can be used in a state of being dissolved in a suitable solvent. As the solvent used at this time, a solvent having a boiling point of 50 ° C. to 200 ° C. can be used, and the solid content concentration in the solution can be 5 to 50%. This solution is applied on a flat substrate such as plastic having a suitable metal such as aluminum deposited to a thickness of about 60 nm, and the solvent is removed to form a coating film having a thickness of about 0.1 to 10 μm.
As the coating method at this time, an appropriate method such as a spin coater or a slit coater can be used, and the solvent can be removed by heating at 50 ° C. to 150 ° C. for about 1 to 30 minutes. After that, pitch width 0.2 μm
An optical recording medium can be formed by irradiating light through a photomask having a track pitch of 1.6 μm with a track pitch of about 0.5 μm, and then performing a post-exposure bake. The conditions of the post-exposure bake at this time are, for example, 50 ° C.
It can be 1 second to 30 minutes at 200 ° C.

<Method of Forming Diffraction Grating> The diffraction grating of the present invention can be formed by an appropriate method, for example, the following method.

The photosensitive refractive index changing composition for forming the diffraction grating can be used in a state of being dissolved in a suitable solvent. As the solvent used at this time, a solvent having a boiling point of 50 ° C. to 200 ° C. can be used, and the solid content concentration in the solution can be 20 to 60%.

This solution was applied onto the surface of an appropriate substrate such as glass and the solvent was removed to form a thin film having a thickness of about 1 to 50 μm. An appropriate method such as a spin coater or a slit coater can be adopted as a coating method, and a solvent can be removed by heating at 50 ° C. to 150 ° C. for about 1 to 30 minutes.

A diffraction grating can be formed by irradiating this coating film with light in a slit shape and then baking after exposure. As a method of irradiating the slit-shaped light, for example, a method as shown in FIG. 2 can be used. FIG. 2 shows a method of irradiating a film-shaped coating film by reflecting parallel irradiation light with a reflector placed obliquely.
The coating film is irradiated with an interference pattern formed by direct light and reflected light. By moving the sample in the direction of the arrow in the drawing at a speed of about 0.1 to 100 μm / min during irradiation, a diffraction grating having an arbitrary period of 0.3 μm or more can be formed as a result. According to this method, a precise refractive index distribution can be given.

As another method of irradiating slit-shaped light, a method of irradiating a coating film formed in the same manner as above with a plurality of radiations from different directions to cause interference, a method of irradiating light through a slit, and the like are available. It can also be used. In either method, a diffraction grating having a desired period can be formed by changing the light irradiation angle or the mirror angle. The post-exposure bake condition is, for example, 50.
The heating can be performed at 1 ° C to 200 ° C for 1 second to 30 minutes.

<Method of Forming Hologram Element> The hologram element of the present invention can be formed by an appropriate method.
For example, the following method can be used.

The photosensitive refractive index changing composition for forming the hologram element can be used in a state of being dissolved in a suitable solvent. As the solvent used at this time,
A solvent having a boiling point of 50 ° C to 200 ° C can be used,
The solid content concentration in the solution can be 20 to 60%.

This solution was applied on the surface of an appropriate substrate such as glass and the solvent was removed to form a thin film having a thickness of about 1 to 50 μm. An appropriate method such as a spin coater or a slit coater can be adopted as a coating method, and a solvent can be removed by heating at 50 ° C. to 150 ° C. for about 1 to 30 minutes.

After irradiating this coating film with an interference pattern, baking is performed after exposure to obtain a recording medium (hologram) in the holographic technique. That is, the image of the object can be recorded on the coating film by causing the signal light transmitted through the object to be recorded and the reference light obtained directly from the same light source to irradiate the coating film and changing the refractive index. The post-exposure bake conditions are, for example, 50 ° C.
The heating can be performed at 200 ° C. for 1 second to 30 minutes.

[0290]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to these.

In the following, the polystyrene reduced weight average molecular weight of the polymer was measured using GPC chromatograph SYSTEM-21 manufactured by Showa Denko KK.

Synthetic Example of Component (A) Synthetic Example 1 o-Phthalaldehyde 5 was used as a monomer in a 1 L flask.
0 parts by weight and 500 parts by weight of tetrahydrofuran were placed in a reaction vessel purged with nitrogen and cooled to -78 ° C. To this, 1.0 part by weight of an n-hexane solution of n-butyllithium (1.5 mol / l) was added, and under a nitrogen atmosphere,
The mixture was stirred under cooling at 78 ° C. for 48 hours.

0.8 part by weight of acetic anhydride and 0.6 part by weight of pyridine were added to the obtained reaction solution in a cooled state, and the mixture was subsequently stirred at -78 ° C for 2 hours. The reaction solution is depressurized under 6
After concentrating to 100 ml by heating at 0 ° C., the mixture was added to 5 L of ion exchange water for 10 minutes. The precipitate was redissolved in 50 parts by weight of tetrahydrofuran, purified by reprecipitation with 5 L of ion-exchanged water, and vacuum dried at 50 ° C. to obtain 45 parts by weight of compound (A-1). The weight average molecular weight of the obtained compound was 26,000.

Synthesis Example 2 o-phthalaldehyde 4 was used as a monomer in a 1 L flask.
5 parts by weight, 5 parts by weight of benzaldehyde, and 500 parts by weight of tetrahydrofuran were charged into a reaction vessel purged with nitrogen and cooled to -78 ° C. To this, 1.0 part by weight of an n-hexane solution of n-butyllithium (1.5 mol / l) was added, and the mixture was stirred under cooling in a nitrogen atmosphere at -78 ° C for 48 hours. 0.8 parts by weight of acetic anhydride and 0.6 parts by weight of pyridine were added to the obtained reaction solution in a cooled state, and the mixture was subsequently stirred at -78 ° C for 2 hours. The reaction solution under reduced pressure,
The whole amount was concentrated to 100 ml by heating at 60 ° C., and then continuously charged into 5 L of ion-exchanged water for 10 minutes. The precipitate was redissolved in 50 parts by weight of tetrahydrofuran, purified by reprecipitation with 5 L of ion-exchanged water, and vacuum dried at 50 ° C. 4
3 parts by weight of compound (A-2) was obtained. The weight average molecular weight of the obtained compound was 15,000.

Synthesis Example 3 o-Phthalaldehyde 4 was used as a monomer in a 1 L flask.
5 parts by weight, 5 parts by weight of glutaraldehyde, and 500 parts by weight of tetrahydrofuran were charged into a reaction vessel purged with nitrogen and cooled to -78 ° C. To this, 1.0 part by weight of an n-hexane solution of n-butyllithium (1.5 mol / l) was added, and the mixture was stirred under cooling in a nitrogen atmosphere at -78 ° C for 48 hours. Acetic anhydride 0.8 was added to the obtained reaction solution.
Parts by weight and 0.6 parts by weight of pyridine are added in a cooled state,
Then, the mixture was stirred at -78 ° C for 2 hours. The reaction mixture was heated at 60 ° C under reduced pressure to concentrate the total amount to 100 ml, and then 5
L ion-exchanged water was continuously added for 10 minutes. The precipitate is redissolved in 50 parts by weight of tetrahydrofuran, and 5 L
Was purified by re-precipitation with ion-exchanged water, and vacuum dried at 50 ° C. to obtain 45 parts by weight of compound (A-3). The weight average molecular weight of the obtained compound was 20,000.

Synthesis Example 4 In a 1 L flask, 25 parts by weight of 4-chloro-o-phthalaldehyde and 500 parts by weight of methylene chloride were added as monomers.
The reaction vessel was purged with nitrogen and cooled to -78 ° C.
To this, 0.1 part by weight of boron trifluoride ether complex was added, and the mixture was stirred under cooling in a nitrogen atmosphere at -78 ° C for 48 hours. 0.8 parts by weight of acetic anhydride and 0.6 parts by weight of pyridine were added to the obtained reaction solution in a cooled state, and the mixture was subsequently stirred at -78 ° C for 2 hours. The reaction solution is depressurized at 60
The whole amount was concentrated to 50 ml by heating at 0 ° C., and then continuously charged into 3 L of ion-exchanged water for 5 minutes. The precipitate was redissolved in 30 parts by weight of tetrahydrofuran, reprecipitated and purified with 3 L of ion-exchanged water, and vacuum dried at 50 ° C. to obtain 46 parts by weight of the compound (A-4). The weight average molecular weight of the obtained compound was 48,000.

Synthesis Example 5 25 parts by weight of 4-bromo-o-phthalaldehyde and 500 parts by weight of methylene chloride as monomers were placed in a 1 L flask.
The reaction vessel was purged with nitrogen and cooled to -78 ° C.
To this, 0.1 part by weight of boron trifluoride ether complex was added, and the mixture was stirred under cooling in a nitrogen atmosphere at -78 ° C for 48 hours. 0.8 parts by weight of acetic anhydride and 0.6 parts by weight of pyridine were added to the obtained reaction solution in a cooled state, and the mixture was subsequently stirred at -78 ° C for 2 hours. The reaction solution is depressurized at 60
The whole amount was concentrated to 50 ml by heating at 0 ° C., and then continuously charged into 3 L of ion-exchanged water for 5 minutes. The precipitate was redissolved in 30 parts by weight of tetrahydrofuran, purified by reprecipitation with 3 L of ion-exchanged water, and vacuum dried at 50 ° C. to obtain 47 parts by weight of compound (A-5). The weight average molecular weight of the obtained compound was 53,000.

Synthesis Example 6 o-Phthalaldehyde 5 was used as a monomer in a 1 L flask.
0 part and 500 parts of tetrahydrofuran were charged into a reaction vessel purged with nitrogen and cooled to -78 ° C. to this,
0.2 part of n-hexane solution of n-butyllithium (1.5 mol / l) was added, and under a nitrogen atmosphere, -78 ° C.
It was stirred for 48 hours under cooling. 0.8 parts by weight of acetic anhydride and 0.6 parts by weight of pyridine were added to the obtained reaction solution in a cooled state, and the mixture was subsequently stirred at -78 ° C for 2 hours. The reaction solution was concentrated under reduced pressure by heating at 60 ° C. to a total volume of 100 ml, and then continuously charged into 5 L of ion-exchanged water for 10 minutes. The precipitate was redissolved in 50 parts by weight of tetrahydrofuran, purified by reprecipitation with 5 L of ion-exchanged water, and vacuum dried at 50 ° C. to obtain 45 g of compound (A-6). The weight average molecular weight of the obtained compound was 110,000.

Synthesis Example 7 In a 500 ml three-necked flask under an argon atmosphere, 1,
33.05 g of 4-benzenethiol and 1,4-di (2-
66.06 g of nitrovinyl) benzene was dissolved in 100 g of N-methylpyrrolidone. To this, a solution of 1.55 g of N-methylmorpholine in 10 g of N-methylpyrrolidone was added with stirring under ice cooling for 1 hour. After the completion of the addition, the reaction solution was left at room temperature to carry out polymerization for 24 hours. After completion of polymerization, tetrahydrofuran-
Reprecipitation purification was performed twice with methanol. The precipitated polymer was separated by filtration and vacuum dried at 50 ° C. to obtain 72.80 g of compound (A-7). The weight average molecular weight of the obtained compound was 5,800.

Synthesis Example 8 49.84 g of terephthaloyl chloride was dissolved in 150 ml of chloroform in a 500 ml three-necked flask under an argon atmosphere, and 1,4-benzenethiol 3 was added thereto.
150 ml of 3.05 g and potassium hydroxide 16.83 g
What was dissolved in ion-exchanged water was added and stirred to perform interfacial polycondensation. After carrying out the reaction for 6 hours, reprecipitation purification was performed twice with tetrahydrofuran-methanol. After filtering off the precipitated polymer, vacuum drying is performed at 50 ° C. to obtain 61.28.
g of compound (A-8) was obtained. The weight average molecular weight of the obtained compound was 27,600.

Synthesis Example 9 A 500 ml three-necked flask was charged with 1, under an argon atmosphere.
33.05 g of 4-benzenethiol, 48.04 g of p-phenylene diisocyanate and 0.12 g of dibutyltin dichloride as a catalyst were added to dimethyl sulfoxide 20.
It was dissolved in 0 g. After completion of the addition, the reaction solution was heated to 60 ° C. and polymerization was carried out for 24 hours. After completion of the polymerization, reprecipitation purification was performed twice with tetrahydrofuran-methanol. The precipitated polymer was separated by filtration and vacuum dried at 50 ° C. to obtain 66.50 g of compound (A-9). The weight average molecular weight of the obtained compound was 15,000.

Synthesis Example 10 4-Nitro-1,3-phenylene dichloroformate 92.42 was placed in a 1 L three-necked flask under an argon atmosphere.
g was dissolved in 400 ml of chloroform and 1,
4-benzenethiol 33.05g and potassium hydroxide 1
A solution prepared by dissolving 6.83 g in 200 ml of ion-exchanged water was added and stirred to carry out interfacial polycondensation. After carrying out the reaction for 6 hours, reprecipitation purification was performed twice with tetrahydrofuran-methanol. The precipitated polymer was separated by filtration and vacuum dried at 50 ° C. to obtain 83.61 g of compound (A-10). The weight average molecular weight of the obtained compound was 32,000.

Synthesis Example 11 49.84 g of terephthalic acid and 57.34 g of phenylmethyldichlorosilane were dissolved in 200 g of N-methylpyrrolidone in a 500 ml three-necked flask under an argon atmosphere. A solution prepared by dissolving 23.73 g of pyridine in 50 g of N-methylpyrrolidone was added to this while stirring under ice cooling for 1 hour. After the addition is completed, the reaction solution is heated to 60 °
The mixture was heated to room temperature and polymerized for 24 hours. After completion of polymerization
The reaction solution was poured into 2 L of methanol to cause precipitation, which was again dissolved in 200 ml of N-methylpyrrolidone and poured into 2 L of methanol for reprecipitation purification. The precipitated polymer was separated by filtration and vacuum dried at 50 ° C. to obtain 70.80 g of compound (A-11). The weight average molecular weight of the obtained compound was 26,000.

Synthesis Example 12 45.66 g of benzaldehyde dimethyl acetal and 42.04 g of methoxyhydroquinone were dissolved in 100 g of diethylene glycol ethyl methyl ether in a 500 ml three-necked flask under an argon atmosphere. P here
-Toluenesulfonic acid 0.06 g was dissolved in diethylene glycol ethyl methyl ether 10 g and added, and the mixture was polymerized with stirring at 100 ° C for 8 hours and then at 130 ° C for 1 hour. At this time, the methanol produced by the reaction was polymerized while distilling off under reduced pressure. After completion of polymerization
The reaction solution was poured into 2 L of methanol for precipitation, dissolved again in 100 ml of diethylene glycol ethyl methyl ether and poured into 2 L of methanol for reprecipitation purification. The precipitated polymer was separated by filtration and vacuum dried at 50 ° C. to obtain 47.93 g of compound (A-12). The weight average molecular weight of the obtained compound was 5,800.

Synthesis Example 13 o-Phthalaldehyde 5 was used as a monomer in a 1 L flask.
0 g and 500 g of tetrahydrofuran were charged into a reaction vessel purged with nitrogen and cooled to -78 ° C. To this, ter
41.83 g of potassium t-butoxide was added, and the mixture was stirred under cooling in a nitrogen atmosphere at -78 ° C for 48 hours. Acetic anhydride 45.67 g and pyridine 35.
38 g was added in a cooled state, followed by stirring at -78 ° C for 2 hours. The reaction solution was concentrated under reduced pressure to 100 ml by heating at 60 ° C., dissolved in 1 L of ethyl acetate, washed 3 times with ion-exchanged water, concentrated with ethyl acetate, and added with 5
Vacuum drying was performed at 0 ° C. to obtain 45 g of compound (A-13). The obtained compound (A-13) had an integral ratio of 1.2-1.3 ppm of a tert-butyl group-derived proton and 7.2-7.7 ppm of an aromatic-derived proton in 1H-NMR. Therefore, the ratio of initiator to monomer is 1
It was one to one.

Synthesis Example 14 49.84 g of terephthaloyl chloride was dissolved in 150 ml of chloroform in a 500 ml three-necked flask under an argon atmosphere, and 1,4-benzenethiol 3 was added thereto.
150 ml of 3.05 g and potassium hydroxide 16.83 g
What was dissolved in ion-exchanged water was added and stirred to perform interfacial polycondensation. After carrying out the reaction for 4 hours, reprecipitation purification was performed twice with tetrahydrofuran-methanol. After filtering off the precipitated compound, it is vacuum dried at 50 ° C. to obtain 56.55.
g of compound (A-14) was obtained. The weight average molecular weight of the obtained compound was 7,600.

Example 1 40 parts by weight of the compound (A-1) as the component (A),
Ladder-like polysilsesquioxane GR as component (B)
650 (manufactured by Showa Denko KK, weight average molecular weight 8,20)
0) 60 parts by weight and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s as the component (C)
1 part by weight of triazine was dissolved in diethylene glycol methyl ethyl ether so that the total solid content concentration was 20% by weight, and then filtered through a membrane filter having a pore size of 0.2 μm to obtain a radiation-sensitive refractive index changing composition. A solution containing was prepared.

<Formation of coating film> After coating the above solution on a silicon substrate using a spinner, prebaking is performed on a hot plate at 90 ° C. for 2 minutes to form a coating film of the radiation-sensitive refractive index changing composition. Formed. <Radiation irradiation treatment> NSR1505i is applied to the obtained coating film.
6A reduction projection exposure machine (manufactured by Nikon Corporation, NA = 0.4)
5, λ = 365 nm), the exposure amount is 20 at the optimum depth of focus.
Radiation irradiation treatment was performed at mJ / cm ² , and then post-exposure bake was performed on a hot plate at 120 ° C. for 2 minutes to obtain a difference in refractive index between a radiation-irradiated portion and a non-radiation-irradiated portion. A 0 μm refractive index pattern was formed. Hereinafter, regarding the refractive index pattern formed here, the radiation irradiated portion is referred to as a “low refractive index portion” and the radiation unirradiated portion is referred to as a “high refractive index portion”.

<Measurement of Refractive Index> The refractive index of each of the high refractive index portion and the low refractive index portion on the silicon substrate at room temperature is
It measured at 633 nm using Auto EL IV NIR III (made by Rudolph Research) ellipsometer. The results are shown in Table 1. <Evaluation of Transparency> A glass substrate having a refractive index pattern formed on the surface thereof was obtained in the same manner as above except that a glass substrate "Corning 1737 (manufactured by Corning)" was used instead of the silicon substrate. Then, the transmittance of the obtained glass substrate was measured at a wavelength of 400 to 800 nm using a spectrophotometer "150-20 type double beam (manufactured by Hitachi, Ltd.)". At this time, if the minimum transmittance exceeds 95%, the transmittance is good, and if it is less than that, it is defective. The results are shown in Table 1.

<Evaluation of Crack Generation> A silicon substrate having a refractive index pattern formed on the surface was subjected to the same procedure as above, and a scanning electron microscope (type “S-2000”, manufactured by Co., Ltd.) was used.
The presence or absence of cracks was confirmed using Hitachi). The results are shown in Table 1.

Example 2 The same procedure as in Example 1 was carried out except that the exposure amount in the radiation irradiation treatment was 300 mJ / cm ^2, and the refractive index and transparency were evaluated. The results are shown in Table 1.

Example 3 70 parts by weight of the compound (A-1) was used as the component (A), and a ladder polysilsesquioxane GR650 30 was used.
Evaluation was carried out in the same manner as in Example 1 except that the weight part was used and the exposure amount in the radiation irradiation treatment and the film thickness of the refractive index pattern were as shown in Table 1. The results are summarized in Table 1.

Example 4 15 parts by weight of the compound (A-1) was used as the component (A), and a ladder polysilsesquioxane GR650 85 was used.
Evaluation was carried out in the same manner as in Example 1 except that the weight part was used and the exposure amount in the radiation irradiation treatment and the film thickness of the refractive index pattern were as shown in Table 1. The results are summarized in Table 1.

Example 5 Evaluations were made in the same manner as in Example 1 except that 40 parts by weight of the compound (A-2) was used as the component (A). The results are summarized in Table 1.

Example 6 Evaluations were made in the same manner as in Example 1 except that 40 parts by weight of the compound (A-3) was used as the component (A). The results are summarized in Table 1.

Example 7 Evaluations were made in the same manner as in Example 1 except that 40 parts by weight of the compound (A-4) was used as the component (A). The results are summarized in Table 1.

Example 8 Evaluations were made in the same manner as in Example 1 except that 40 parts by weight of the compound (A-5) was used as the component (A). The results are summarized in Table 1.

Example 9 Evaluation was carried out in the same manner as in Example 1 except that 1 part by weight of 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate was used as the component (C).
The results are summarized in Table 1.

Example 10 Evaluations were made in the same manner as in Example 1 except that 1 part by weight of diphenyliodonium trifluoroacetate was used as the component (C). The results are summarized in Table 1.

[0320]

[Table 1]

Example 11 As component (A), 50 parts by weight of compound (A-7),
As component (B), ladder-like polysilsesquioxane G
50 parts by weight of R650 and 5 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one as the component (C) make the total solid content concentration 20%. Thus, it was dissolved in diethylene glycol ethyl methyl ether and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution.

<Formation of Coating Film> The same procedure as in Example 1 was carried out. <Radiation Irradiation Treatment and PEB Treatment> On the obtained coating film, NSR1505i6A reduction projection radiation irradiator (manufactured by Nikon Corporation, NA = 0.45, λ = 365 nm)
The radiation irradiation processing was performed at the optimum depth of focus. Then, PEB treatment was performed for 2 minutes to form a refractive index pattern having a thickness of 3.0 μm and having a difference in refractive index between the irradiated and unirradiated portions of the refractive index changing composition. The radiation dose and PEB treatment temperature are shown in Table 2. Hereinafter, regarding the refractive index pattern formed here, the radiation irradiated portion is referred to as a “low refractive index portion” and the radiation unirradiated portion is referred to as a “high refractive index portion”. <Measurement of refractive index>, <Evaluation of transparency>, and <Evaluation of crack occurrence> were all performed in the same manner as in Example 1.

Example 12 Evaluation was carried out in the same manner as in Example 11 except that 50 parts by weight of the compound (A-8) was used as the component (A). The results are summarized in Table 2.

Example 13 Evaluations were made in the same manner as in Example 11 except that 50 parts by weight of the compound (A-9) was used as the component (A). The results are summarized in Table 2.

Example 14 Evaluations were made in the same manner as in Example 11 except that 50 parts by weight of the compound (A-10) was used as the component (A). The results are summarized in Table 2.

Example 15 As component (B), ladder-like polysilsesquioxane G
R100 (manufactured by Showa Denko KK, weight average molecular weight 8,50)
Evaluation was carried out in the same manner as in Example 11 except that 50 parts by weight of 0) was used. The results are summarized in Table 2.

Example 16 As component (B), ladder-like polysilsesquioxane G
R908 (manufactured by Showa Denko KK, weight average molecular weight 9.00)
Evaluation was carried out in the same manner as in Example 11 except that 50 parts by weight of 0) was used. The results are summarized in Table 2.

Example 17 As component (B), ladder-like polysilsesquioxane G
R950 (manufactured by Showa Denko KK, weight average molecular weight 9,20)
Evaluation was carried out in the same manner as in Example 11 except that 50 parts by weight of 0) was used. The results are summarized in Table 2.

[0329]

[Table 2]

Example 18 50 parts by weight of the compound (A-11) as the component (A),
Ladder-like polysilsesquioxane GR as component (B)
650 50 parts by weight, and 2- (4) as the component (C)
1 part by weight of -methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine was dissolved in diethylene glycol ethyl methyl ether so that the total solid content concentration was 20%, and then the pore size was 0.2 μm. The solution was filtered with a membrane filter to prepare a solution of the radiation-sensitive refractive index changing composition.

<Formation of coating film> After coating the above solution on a silicon substrate using a spinner, prebaking is performed on a hot plate at 90 ° C. for 2 minutes to form a coating film of the radiation-sensitive refractive index changing composition. Was formed.

<Formation of Refractive Index Pattern> On the coating film obtained as described above, NSR1505i6A reduction projection radiation irradiator (manufactured by Nikon Corporation, NA = 0.45, λ = 3)
65 nm) at the optimum depth of focus, the exposure amount is 50 mJ /
Radiation irradiation treatment was performed in cm ² . Then, by performing a post-exposure bake treatment at 130 ° C. for 2 minutes, a thickness of 3.0 which has a difference in refractive index between the radiation-irradiated portion and the radiation-unirradiated portion.
A μm refractive index pattern was formed. Hereinafter, regarding the refractive index pattern formed here, the radiation irradiated portion is referred to as a “low refractive index portion” and the radiation unirradiated portion is referred to as a “high refractive index portion”.

<Measurement of Refractive Index> The refractive index of each of the low refractive index portion and the high refractive index portion of the refractive index pattern formed above was measured at 633 nm using an Auto EL IV NIR III (manufactured by Rudolph Research) ellipsometer. It was measured at. The results are shown in Table 3.

<Evaluation of Transparency> A refractive index pattern was formed on the glass substrate in the same manner as above except that the glass substrate "Corning 1737 (manufactured by Corning)" was used instead of the silicon substrate. Hereinafter, also in the refractive index pattern on the glass substrate formed here, the radiation irradiated portion is referred to as a “low refractive index portion” and the radiation unirradiated portion is referred to as a “high refractive index portion”. Then, with respect to the glass substrate having this refractive index pattern, the transmittance of each of the low refractive index portion and the high refractive index portion was 400 using a spectrophotometer "150-20 type double beam (manufactured by Hitachi, Ltd.)". ~ 800 nm
Was measured at the wavelength of. At this time, if the minimum transmittance exceeds 95%, the transmittance is good, and if it is less than that, it is defective. The results are shown in Table 3.

<Stabilizing Treatment> As component (D), 150 ml of phenylglycidyl ether (containing 0.1 mmol of tetrabutylammonium bromide as a reaction catalyst) was heated to 100 ° C., and the silicon formed as described above was added thereto. After dipping the refractive index pattern on the substrate and the glass substrate at 100 ° C. for 2 minutes, 1
Washed for minutes. Then, Canon PLA-501F
4.5mW for the entire pattern without using a filter
/ Cm ^{2 for} 1 minute of re-exposure treatment, and further heated in an oven at 200 ° C. for 10 minutes to stabilize the refractive index pattern.

<Evaluation of Refractive Index and Transparency> With respect to the refractive index pattern on the silicon substrate subjected to the above-mentioned stabilization treatment, the refractive index of the low refractive index portion and the high refractive index portion were measured in the same manner as above. I went. The results are shown in Table 4. Further, with respect to the refractive index pattern on the stabilized glass substrate, the transparency of the low refractive index portion and the high refractive index portion was measured in the same manner as above. The results are shown in Table 4.

<Evaluation of Stability of Refractive Index Pattern> The refractive index pattern on the silicon substrate subjected to the above-mentioned stabilization treatment,
And the refractive index pattern on the glass substrate, Can
On PLA-501F, without using a filter, the entire surface of the pattern was subjected to an exposure treatment at 4.5 mW / cm ^{2 for} 30 minutes to accelerate the radiation irradiation. With respect to the refractive index pattern on the silicon substrate subjected to this treatment, the refractive index of the low refractive index portion and the high refractive index portion were measured in the same manner as above. The results are shown in Table 4. Further, with respect to the refractive index pattern on the stabilized glass substrate, the transparency of the low refractive index portion and the high refractive index portion was measured in the same manner as above. The results are shown in Table 4.

<Evaluation of Crack Generation Before and After Stabilization Treatment> The presence or absence of cracks in the refractive index pattern was confirmed in the same manner as in Example 1 before and after the stabilization treatment. The results are shown in Tables 3 and 4.

Example 19 As the component (A), 50 parts by weight of the compound (A-12) was used, and the temperature of the post-exposure bake in the step (formation of the refractive index pattern) was as shown in Table 3, Evaluation was carried out in the same manner as in Example 18 except that the type of component (D) in Stabilization treatment) and the stabilization treatment temperature were as shown in Table 4. The results are summarized in Tables 3 and 4.

Example 20 As the component (A), 50 parts by weight of the compound (A-1) was used, and the radiation dose in the step (formation of the refractive index pattern) was as shown in Table 3. Evaluation was carried out in the same manner as in Example 18 except that the type of component (D) in (4) and the stabilization treatment temperature were as shown in Table 4. The results are summarized in Tables 3 and 4.

Example 21 As component (A), 50 parts by weight of compound (A-8),
As the component (C), 5 parts by weight of N- (2-nitrobenzyloxycarbonyl) pyrrolidine was used, and the radiation dose in the step (formation of the refractive index pattern) was as shown in Table 3, and the step (stabilization treatment) The evaluation was performed in the same manner as in Example 18 except that the type of the component (D) in (4) was changed as shown in Table 4. The results are summarized in Tables 3 and 4.

Example 22 As component (C), 1 part by weight of 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate was used, and the radiation dose in the step (formation of refractive index pattern) was as shown in Table 3. Evaluation was performed in the same manner as in Example 18 except that the above was performed. The results are summarized in Tables 3 and 4.

Example 23 Evaluations were made in the same manner as in Example 21 except that the radiation dose in the step (formation of the refractive index pattern) was as shown in Table 3. The results are summarized in Tables 3 and 4.

[0344]

[Table 3]

[0345]

[Table 4]

However, in Table 4, the symbols of the component (D) represent the following. D-1; Phenylglycidyl ether (10 mol% tetrabutylammonium bromide added) D-2: 1% aqueous solution of p-xylylenediamine D-3; 3-phenoxypropylene sulfide (10 m
ol% tetrabutylammonium bromide added)

Example 24 50 parts by weight of the compound (A-11) as the component (A),
Ladder-like polysilsesquioxane GR as component (B)
650 (manufactured by Showa Denko KK, weight average molecular weight 8,20)
0) 50 parts by weight, and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s as the component (C)
After dissolving 1 part by weight of triazine and 10 parts by weight of bisphenol A diglycidyl ether as the component (D) in diethylene glycol ethyl methyl ether so that the total solid content concentration becomes 20%, the pore size is 0.2 μm.
m membrane filter to prepare a solution of the refractive index changing composition. The formation of a coating film, the formation of a refractive index pattern, the measurement of the refractive index, the evaluation of transparency, and the evaluation of the refractive index and transparency were all performed in the same manner as in Example 18.

<Stabilizing Treatment> The refractive index patterns on the silicon substrate and the glass substrate formed as described above were measured at 150 ° C. (the component (A) did not decompose and the components (A) and (D)). Heat treatment was performed for 2 minutes at a temperature at which the components reacted. Then, with a Canon PLA-501F, 4.5 mW /
Re-exposure treatment was carried out at 1 cm ^{2 for} 1 minute, followed by heating in an oven at 200 ° C. for 10 minutes to stabilize the refractive index pattern.

<Re-exposure and heat treatment> Stabilized above
For each treated refractive index pattern, Ca
Pattern without filter with nonPLA-501F
4.5mW / cm for the entire surface ²Radiation for 1 minute at
And then heat in an oven at 200 ° C for 10 minutes
did.

<Evaluation of stability after re-exposure and heat treatment> For the refractive index pattern on the re-exposed and heat-treated silicon substrate, the low-refractive-index portion and the high-refractive-index portion were processed in the same manner as in <Measurement of refractive index> The refractive index of each part was measured, and the stability of the refractive index against re-exposure and heating was evaluated. For the refractive index pattern on the re-exposed and heat-treated glass substrate, the transparency of the low refractive index part and the high refractive index part was measured in the same manner as in the above <Evaluation of transparency>, and re-exposed and heated. The stability of transparency was evaluated. The results are shown in Tables 5 and 6.

<Evaluation of Crack Generation Before and After Stabilization Treatment> The presence or absence of cracks in the refractive index pattern was confirmed in the same manner as in Example 1 before and after the stabilization treatment. The results are shown in Tables 5 and 6.

Example 25 As component (A), 50 parts by weight of compound (A-12) was used, and the temperature of the post-exposure bake in the step (formation of refractive index pattern) was as shown in Table 5, Evaluation was performed in the same manner as in Example 24 except that the treatment temperature in the chemical treatment) was set as shown in Table 6. The results are summarized in Tables 5 and 6.

Example 26 As the component (A), 50 parts by weight of the compound (A-13) was used, and the radiation dose in the step (formation of the refractive index pattern) was as shown in Table 5, and the step (stabilization treatment) was performed. Evaluation was carried out in the same manner as in Example 24 except that the treatment temperature in 4) was set as shown in Table 6. The results are summarized in Tables 5 and 6.

Example 27 As the component (A), 50 parts by weight of the compound (A-14),
As the component (C), 5 parts by weight of N- (2-nitrobenzyloxycarbonyl) pyrrolidine was used, and the radiation dose in the step (formation of the refractive index pattern) was as shown in Table 5, and the step (stabilization treatment) The evaluation was performed in the same manner as in Example 24 except that the treatment temperature in Example 1 was set as shown in Table 6. The results are summarized in Tables 5 and 6.

Example 28 As component (D), 1,4-bis (4,5-dihydro-)
Using 10 parts by weight of 2-oxazolyl) benzene, the radiation dose in the step (formation of the refractive index pattern) was as shown in Table 5, and the treatment temperature in the step (stabilization treatment) was as shown in Table 6. The evaluation was performed in the same manner as in Example 24 except for the above. The results are shown in Table 5 and Table 6.
Summarized in.

Example 29 As component (D), 1,4-bis (4,5-dihydro-
Using 10 parts by weight of 2-oxazolyl) benzene, the radiation dose in the step (formation of the refractive index pattern) was as shown in Table 5, and the treatment temperature in the step (stabilization treatment) was as shown in Table 6. The evaluation was performed in the same manner as in Example 27 except for the above. The results are shown in Table 5 and Table 6.
Summarized in.

[0357]

[Table 5]

[0358]

[Table 6]

Example 30 50 parts by weight of the compound (A-11) as the component (A), 50 parts by weight of ladder polysilsesquioxane GR650, and 4-phenylthiophenyldiphenylsulfonium trifluoromethane as the component (C). 1 part by weight of sulfonate was dissolved in diethylene glycol ethyl methyl ether so that the total solid content concentration was 20%, and then filtered through a membrane filter having a pore size of 0.2 μm,
A refractive index changing composition was prepared.

<Formation of coating film> The above solution was coated on a silicon substrate using a spinner, and then prebaked at 100 ° C for 2 minutes on a hot plate to form a coating film of the refractive index changing composition. . <Formation of refractive index pattern>, <Stabilization treatment>, <Measurement of refractive index> and <Evaluation of transparency>
Was performed in the same manner as in Example 18.

<Measurement of Porosity Using Mercury Porosimeter> The porosities of the low-refractive index portion and the high-refractive index portion of the refractive index pattern formed above were measured by the mercury porosimeter (trade name).
Shimadzu auto pore 9200, minimum measurable pore size 3
4Å) was used for the measurement.

<Measurement of Void Hole Distribution by BJH Method> COU is used to measure the hole distribution in the low refractive index portion of the refractive index pattern formed above.
OMNISORP 100/360 S made by LTER
It measured by BJH method using ERIES. 100 nm
Table 8 shows the numbers of the above pores.

<Measurement of Pore Diameter by Electron Microscope Observation> The pore diameter of each of the low refractive index portion and the high refractive index portion of the refractive index pattern formed above was measured by a transmission electron microscope at 10 μm ² in an arbitrary observation range. Per diameter 1
The number of holes having a size of 00 nm or more was measured. <Evaluation of crack occurrence> was performed in the same manner as in Example 1. The results are shown in Table 7.

Example 31 As the component (A), 50 parts by weight of the compound (A-12) was used, and the types of the component (D) and the stabilization treatment temperature in the step (stabilization treatment) are shown in Table 7. Evaluation was performed in the same manner as in Example 30 except that the above was performed. The results are summarized in Tables 7 and 8.

Example 32 As the component (A), 50 parts by weight of the compound (A-13) was used, and the radiation dose in the step (formation of the refractive index pattern) was as shown in Table 7. Evaluation was carried out in the same manner as in Example 30 except that the type of component (D) in () and the stabilization treatment temperature were as shown in Table 7. The results are summarized in Tables 7 and 8.

Example 33 As the component (A), 50 parts by weight of the compound (A-14),
Example 30 except that 5 parts by weight of N- (2-nitrobenzyloxycarbonyl) pyrrolidine was used as the component (C) and the radiation dose in the step (formation of the refractive index pattern) was as shown in Table 7. It evaluated similarly. The results are summarized in Tables 7 and 8.

[0367]

[Table 7]

However, in Table 7, the symbols of the component (D) represent the following. D-4: Phenyl glycidyl ether (10 mol% tetrabutylammonium bromide added) D-5: 1% aqueous solution of p-xylylenediamine

[0369]

[Table 8]

Example 34 (Preparation of GI optical fiber (1)) As component (A), 50 parts by weight of compound (A-6),
Ladder-like polysilsesquioxane GR as component (B)
650 50 parts by weight, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate as component (C) 1 part by weight, and further as an ultraviolet absorber 2
-(2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl) -2H-benzotriazol 1.
5 parts by weight were dissolved in methyl ethyl ketone so that the total solid content concentration was 70%. This solution was used as a stock solution of fiber, and after defoaming, it was extruded from an injection port with a pore size of 1.0 mm at 1 m / min, and a 250 mW super high pressure mercury lamp (USHIO INC. Spot cure, i-line) Illuminance: 6.7 mW / cm ² ) with a ring type light guide (inner diameter 55 mm) manufactured by Nippon PII Co., Ltd.
Using, to irradiate the fiber uniformly from around the fiber,
Then, the irradiation width of the infrared lamp was set to 10 cm so that the fiber was heated at 200 ° C. for 5 seconds, and the fiber was heated.

By carrying out light irradiation from the surroundings, a large amount of acid generated from the component (C) is distributed near the surface of the fiber, and the decomposition of the component (A) is gradually reduced by heating from the vicinity of the surface to the inside. A GI type optical fiber having a distribution in which the refractive index decreases parabolicly from the central axis to the periphery was manufactured. When measured with an interference refractometer, the maximum refractive index difference Δn between the center and the periphery was 0.09.

Example 35 (Preparation of GI optical fiber (2)) A GI optical fiber was prepared in the same manner as in Example 34 except that 50 parts by weight of the compound (A-5) was used as the component (A). . When measured with an interference refractometer, the maximum refractive index difference Δn between the center and the periphery was 0.11.

Example 36 (Production of GI type optical fiber (3)) 1 part by weight of 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine was used as the component (C). A GI type optical fiber was produced in the same manner as in Example 34 except for the above. When measured with an interference refractometer,
The maximum refractive index difference Δn between the center and the periphery was 0.09.

Example 37 (Production of GRIN Lens (1)) The GI optical fibers produced in Examples 34 to 36 were cut into short lengths to obtain GRIN lenses having a continuous refractive index distribution from the center to the periphery. It was

Example 38 (Production of GRIN Lens (2)) As the component (A), 50 parts by weight of the compound (A-2),
Ladder-like polysilsesquioxane GR as component (B)
650 50 parts by weight, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate as component (C) 1 part by weight, and further as an ultraviolet absorber 2
-(2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl) -2H-benzotriazol 1.
5 parts by weight were dissolved in methyl ethyl ketone so that the total solid content concentration was 70%, and then a disk-shaped sample having a diameter of 2 cm and a thickness of 5 mm was obtained by hot pressing under reduced pressure.
As shown in FIG. 1, the irradiation device is provided with a diaphragm 2 that can be opened and closed in front of a disk-shaped sample 1, and the irradiation device 3 closes the diaphragm 2 with ultraviolet rays 4 having a wavelength of 365 nm and an illuminance of 30 mW / cm ^2. Irradiation while gradually opening from 5
The shutter speed was adjusted so that the aperture 2 was completely opened in a second, the irradiation was terminated after 5 seconds, and then a post-exposure bake was performed at 120 ° C. for 2 minutes. As a result, a disc-shaped optical molded body having a continuously increasing refractive index from the central portion to the peripheral portion was obtained. The refractive index difference was 0.08, and it became a GRIN lens having a concave lens ability, and showed a possibility as a lens for myopia spectacles.

Example 39 (Production of GRIN lens (3)) A disk-shaped sample was obtained in the same manner as in Example 37.
A 250 mW super high pressure mercury lamp (USHIO INC. Spot cure, i line illuminance: 6.7 mW /
cm ² ) is irradiated for 20 seconds using a ring type light guide (inner diameter 55 mm) manufactured by Nippon PII Co., Ltd., and 1
A post-exposure bake was performed at 20 ° C. for 2 minutes. As a result, a disk-shaped optical molded body having a continuously decreasing refractive index from the central portion to the peripheral portion was obtained. The refractive index difference was 0.08, and a GRIN lens having a convex lens function was obtained.

Example 40 (Production of GI Type Optical Waveguide) As the component (A), 50 parts by weight of the compound (A-2),
Ladder-like polysilsesquioxane GR as component (B)
650 50 parts by weight and 1 part by weight of 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate as the component (C) make the total solid content concentration 40%.
After being dissolved in diethylene glycol ethyl methyl ether so as to be, the mixture was filtered through a membrane filter having a pore size of 1.0 μm to prepare a solution (S-1) containing the photosensitive refractive index changing composition. Further, 100 parts by weight of ladder-like polysilsesquioxane GR650 (weight average molecular weight 8,200) used as the component (B) and SI-L150 (manufactured by Sanshin Chemical Co., Ltd.) as a thermal acid generator 1 part by weight. Part and a solution in which diethylene glycol ethyl methyl ether was dissolved so that the total solid content concentration was 40% (S-2)
Was prepared.

First, the solution (S-2) was applied on the surface of a silicon substrate by a spin coater, dried at 70 ° C. for 10 minutes, and then irradiated with ultraviolet rays having a wavelength of 365 nm and an illuminance of 4.0 mW / cm ² for 5 seconds. Was performed to form a lower clad layer having a thickness of 10 μm. Next, the solution (S-1) was applied onto the lower clad layer by a spin coater and dried at 70 ° C. for 10 minutes to form an intermediate layer having a thickness of 10 μm, and then a width of 4 to 2 was applied.
Ultraviolet rays having a wavelength of 365 nm and an illuminance of 4.0 mW / cm ² were irradiated for 10 seconds using a photomask having an optical waveguide pattern of 0 μm. Then, post-exposure bake was performed at 120 ° C. for 2 minutes. At this time, the unexposed portion becomes the core portion and the exposed portion becomes the side clad layer. The solution (S-2) Following on this was coated by a spin coater, dried for 10 minutes at 70 ° C., after forming the upper cladding layer having a thickness of 10 [mu] m, the wavelength 365 nm, the ultraviolet intensity 4.0 mW / cm ² on the entire surface After irradiating for 5 seconds, a post-exposure bake was performed at 120 ° C. for 2 minutes to manufacture an optical waveguide. The refractive index of light having a wavelength of 1550 nm of the formed upper, side and lower clad layers was 1.42. On the other hand, the refractive index of light having a wavelength of 1,550 nm in the core layer was 1.50, and the maximum refractive index difference Δn was 0.08. The optical waveguide obtained here contains the photo-acid generator in the upper and lower parts,
At the interface between the core layer and the upper and lower clad layers, slightly generated acid diffuses. As a result, the refractive index distribution is generated at the interface between the core layer and the clad layer in the upper portion, the side portion, and the lower portion, and the obtained optical waveguide is of the GI type. With respect to the thus obtained optical waveguide, the waveguide loss was obtained by measuring the amount of light emitted from the other end when light having a wavelength of 1,300 nm was made incident from one end of the waveguide. 1 dB
/ Cm or less.

Example 41 (Preparation of Optical Recording Medium) As component (A), 50 parts by weight of compound (A-2),
Ladder-like polysilsesquioxane GR as component (B)
50 parts by weight of 650 and 1 part by weight of 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate as the component (C) make the total solid content concentration 20%.
After being dissolved in diethylene glycol ethyl methyl ether so as to be, the mixture was filtered through a membrane filter having a pore size of 0.2 μm to prepare a solution containing the photosensitive refractive index changing composition. This was applied on a flat polycarbonate substrate having an aluminum reflection film deposited to a thickness of 60 nm by a sputtering method with a spin coater and dried at 80 ° C. for 2 minutes to form a refractive index change layer having a thickness of 3.0 μm.
After that, the track pitch is 1.6 μm and the pitch width is 0.5 μm.
illuminance of 40 mW / c at a wavelength of 365 nm through a mask of m
Ultraviolet irradiation of m ² was performed for 5 seconds, and post-exposure baking was performed at 120 ° C. for 2 minutes. As a result, the difference in the refractive index obtained between the exposed portion and the unexposed portion was 0.08 at 633 nm, which was sufficiently readable as an optical recording medium.

Example 42 (Production of Optical Integrated Circuit) As the component (A), 50 parts by weight of the compound (A-2),
Ladder-like polysilsesquioxane GR as component (B)
650 50 parts by weight and 1 part by weight of 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate as the component (C) make the total solid content concentration 33%.
After being dissolved in diethylene glycol ethyl methyl ether so as to be, the mixture was filtered through a membrane filter having a pore size of 1.0 μm to prepare a solution containing the photosensitive refractive index changing composition. This was coated on the surface of a glass substrate with a spin coater and dried at 70 ° C. for 10 minutes, and then 100 μm
Through an m-width mask, wavelength 365nm, illuminance 4.0m
Irradiate W / cm ² of UV light for 5 seconds, and keep at 120 ℃ for 2
A post exposure bake was performed for a minute. As a result, an optical integrated circuit having a refractive index pattern of 100 μm could be obtained.

Example 43 (Production of Light Diffraction Grating) Using the solution prepared in Example 40, 2 cm × 1 cm ×
A 10 μm film-like sample was prepared. This sample was irradiated with ultraviolet rays having a wavelength of 365 nm and an illuminance of 4.0 mW / cm ² . As the irradiation method, as shown in FIG. 2, the irradiation light from the irradiation device 8 was converted into parallel light 9 which was reflected by the reflection plate 7 placed at 45 ° and applied to the film sample 5 on the stage 6. The sample is illuminated with an interference pattern formed from the reflected light and the directly illuminated light. The sample was moved at a speed of 1 μm / min in the direction of the arrow with the irradiation, and as a result, an optical diffraction grating having a period of 0.5 μm was obtained.

Example 44 (Production of Hologram) Parallel light having a wavelength of 365 nm and an illuminance of 4.0 mW / cm ² was split into two optical paths by a half mirror, one of which passed through a transparent object to be signal light, and the other of which was referred to. Interfere with light,
The same optical molding as in Example 42 was irradiated with the interference pattern. By irradiating the obtained optical molded product with reproduction illumination light, an object image recorded with high resolution could be confirmed.

[Brief description of drawings]

FIG. 1 is a schematic view of an apparatus for performing light irradiation when forming a lens from the refractive index changing composition of the present invention.

FIG. 2 is a schematic view of an apparatus for performing light irradiation when forming a diffraction grating from the refractive index changing composition of the present invention.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 27, 2002 (2002.9.2)
7)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0185

[Correction method] Change

[Correction content]

As the above amino compound, ammonia,
Trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, triphenylamine, tribenzylamine, aniline, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,3- Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminoontan, 1,9-diaminononane, 1,10-diamino Decane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,4-
Diaminocyclohexane, 1,3-cyclohexanebis (methylamine), 2,2 ', 2 "-triaminotriethylamine, 1,4-diamino-2,2,3,3-tetrafluoropentane, 1,5-diamino- 2, 2, 3,
3,4,4-hexafluoropentane, melamine, benzoguanamine, acetoguanamine, acryloguanamine,
Paramine, amidole, m-phenylenediamine, p-
Phenylenediamine, p, p'-diaminodiphenylmethane, diaminodiphenylsulfone, 1,8-diaminonaphthalene, 3,5-diamino-1,2,4-triazole, 2-chloro-4,6-diamino-S-triazine, 2,6-diaminopyridine, 3,3′-diaminobenzidine, bis (4-aminophenyl) ether, m-
Xylylenediamine, p-xylylenediamine, 1,
2,4,5-benzenetetramine, 2,4-diamino-
1,3,5-triazine, 4,4'-diaminobenzophenone, 3,3 ', 4,4'-tetraaminobenzophenone, triaminobenzene, 4,4'-thiodianiline, 2,3,5,6-tetrabromo -P-xylylenediamine, 2,3,5,6-tetrachloro-p-xylylenediamine, 4,5-methylenedioxy-1,2-phenylenediamine, 2,2'-bis (5-aminopyridyl) ) Sulfide etc. can be mentioned.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0186

[Correction method] Change

[Correction content]

Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cycloaliphatic epoxy resin,
Examples thereof include bisphenol A type epoxy compounds and aliphatic polyglycidyl ethers.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0227

[Correction method] Change

[Correction content]

Specifically, for example, alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, ethylene glycol and propylene glycol; ethers such as tetrahydrofuran;
Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether Diethylene glycols; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether Propylene glycol alkyl ether acetates such as teracetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether pro Propylene glycol alkyl ether propionates such as pionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;

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[Document name to be amended] Statement

[Correction target item name] 0245

[Correction method] Change

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Examples of such a solvent include water; methanol, ethanol, iso-propanol, n-propanol, n-butanol, iso-butanol, te.
Alcohols such as rt-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol; ethers such as diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methyl cellosolve acetate, ethyl cellosolve Ethylene glycol alkyl ether acetates such as acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether and propylene glycol ethyl ether; Propylene glycol methyl ether Propylene glycol alkyl ether acetates such as teracetate and propylene glycol ethyl ether acetate; propylene such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate Glycol alkyl ether propionates ; toluene,
Aromatic hydrocarbons such as xylene; Aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane; Methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl amyl ketone, 4-hydroxy-4-methyl-2- Ketones such as pentanone; and ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, butyl hydroxyacetate, ethyl lactate, propyl lactate, butyl lactate , Methyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, ethyl methoxyacetate, butyl methoxyacetate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, butyl 2-ethoxypropionate, 2-butoxyp Butyl acid, 3-methoxy propionic acid butyl, 3-ethoxypropionate, butyl,
Esters such as butyl 3-propoxypropionate and butyl 3-butoxypropionate; trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene, hexafluorobenzene, hexafluorocyclohexane, perfluorodimethylcyclohexane, perfluoromethylcyclohexane , Octafluorodecalin, 1,1,2-trichloro-1,2,2-trifluoroethane, and other fluorine atom-containing solvents.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 5/18 G02B 5/18 4J002 6/00 391 6/00 391 6/12 G03F 7/004 521 G03F 7 / 004 521 G03H 1/02 G03H 1/02 G02B 6/12 N (72) Inventor Atsushi Kumano 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Corporation (72) Inventor Nobuo Bessho Chuo-ku, Tokyo Tsukiji 2-chome 11-24 F term in JSR Co., Ltd. (reference) 2H025 AA00 AB14 AC08 BE00 CB33 CC20 2H047 PA02 PA15 PA24 PA28 QA05 2H049 AA12 AA34 AA43 AA59 2H050 AA13 AB42Z 2K008 AA04 DD12 FF17 CD02CD05 CD01 CD02 CD01 CD02 CD01 CD02 CD01 CD02 CD01 CD02 CD01 CD02 CD01 CD02 CD01 CD02 CD01 CG02W CH00W CH01W CK05W CN01W CN06W CP03W CP03X CP19W CQ03W DF007 EB116 EH036 EL027 EL057 EN027 EN037 EN047 EN067 E N077 EN087 EN127 EN136 ER007 ET006 ET007 EU027 EU047 EU167 EU186 EU187 EU227 EU236 EV066 EV087 EV217 EV246 EV296 EV307 EW047 EW067 EW126 EX027 EX037 EX047 EX067 EX077 EX087 EY016 FD03Y FD037 FD050 FD206 FD310 GP03

Claims (17)

[Claims] 1. A refractive index lower than that of the decomposable compound (A) selected from the group consisting of (A) decomposable compound, (B) ladder-type polysilsesquioxane, its hydrolyzate and its condensate. A radiation-sensitive refractive index changing composition comprising a non-degradable compound, (C) a radiation-sensitive decomposing agent, and (D) a stabilizer. 2. The composition according to claim 1, wherein the refractive index of the radiation-irradiated portion is 0.02 or more in maximum difference from the refractive index of the radiation-unirradiated portion. 3. The refractive index n _B of the non-decomposable compound (B) is
The composition according to claim 1 or 2, wherein the decomposable compound (A) has a refractive index n _A and the following formula (1): n _A −n _B ≧ 0.05 (1). object. 4. The composition according to claim 1, wherein (A) the decomposable compound is an acid decomposable compound, and (C) the radiation-sensitive decomposing agent is a radiation-sensitive acid generator. object. 5. The acid-decomposable compound (A) is represented by the following formula (1):
(8) [Chemical formula 1] (In the formula (1), R ¹ is an alkylene group, an alkylenearylenealkylene group or an arylene group, and R ² is an alkylene group, an alkylenearylenealkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group.) Chemical 2] (In the formula (2), M is Si or Ge, and R ³
Is an alkylene group, an alkylenearylene alkylene group,
An arylene group, an alkylsilylene group or an alkylgermylene group, R ⁴ is an oxygen atom, an alkylene group, an alkylenearylenealkylene group, an arylene group or a single bond, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently Is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a thioalkyl group, and m is an integer of 0 to 2. ) [Chemical 3] (In the formula (3), R ⁹ and R ¹⁰ are each independently an alkylene group, an alkylenearylenealkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group.) (In the formula (4), R ¹¹ is an oxyalkylene group or a single bond, and R ¹² is a hydrogen atom, an alkyl group, an alkylenearylenealkylene group or an aryl group.) (In the formula (5), R ¹³ is a hydrogen atom, an alkyl group or an aryl group.) (In the formula (6), R ¹⁴ is an alkylene group or a structure represented by the following formula (6) -1, (6) -2 or (6) -3). (In formula (6) -1, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸
Are independently of each other a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a mercapto group, a carboxyl group, an alkoxyl group having 1 to 6 carbon atoms, and a carbon atom having 1 to 6 carbon atoms. Alkylthio group, halogenated alkyl group having 1 to 6 carbon atoms, halogenated alkoxyl group having 1 to 6 carbon atoms, halogenated alkylthio group having 1 to 6 carbon atoms,
C1-6 hydroxyalkyl group, C1-6 mercaptoalkyl group, C1-6 hydroxyalkoxyl group, C1-6 mercaptoalkylthio group, C6-10 aryl group or carbon Number 7-11
Is an aralkyl group. ) [Chemical 8] (In the formula (6) -2, R ¹⁹ is an alkylene group.) (In the formula (6) -3, R ²⁰ is an alkylene group.) (In the formula (7), R ²¹ is an alkylene group, an alkylenearylene alkylene group or an arylene group.) (In the formula (8), R ²² , R ²³ , R ²⁴ and R ²⁵ are independently of each other a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms,
Chlorine atom, bromine atom, iodine atom, hydroxyl group, mercapto group, carboxyl group, alkoxyl group having 1 to 6 carbon atoms,
Alkylthio group having 1 to 6 carbon atoms, halogenated alkyl group having 1 to 6 carbon atoms, halogenated alkoxyl group having 1 to 6 carbon atoms, halogenated alkylthio group having 1 to 6 carbon atoms, hydroxyalkyl having 1 to 6 carbon atoms A group, a mercaptoalkyl group having 1 to 6 carbon atoms, a hydroxyalkoxyl group having 1 to 6 carbon atoms, a mercaptoalkylthio group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 11 carbon atoms is there. The composition according to claim 4, which contains at least one compound having at least one structure selected from the group consisting of the structures represented by any of (1) to (5). 6. The composition according to claim 1, wherein (A) the decomposable compound is a base-decomposable compound, and (C) the radiation-sensitive decomposing agent is a radiation-sensitive base generator. object. 7. The decomposable compound (A) is represented by the following formula (9):
(12) (In the formula (9), R ²⁶ is an alkylene group, an aralkylene group or an arylene group, R ²⁷ is an alkylene group,
An aralkylene group, an arylene group, an alkylenearylenealkylene group, an alkylsilylene group or an alkylgermylene group, wherein R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or A thioalkyl group and i and j
Are independently 0 or 1. ) [Chemical 13] (In the formula (10), R ³² is an alkylene group, an aralkylene group or an arylene group, and R ³³ is an alkylene group, an aralkylene group, an arylene group, an alkylenearylenealkylene group, an alkylsilylene group or an alkylgermylene group.) [Chemical 14] (In the formula (11), R ³⁴ and R ³⁵ are each independently an alkylene group, an aralkylene group, an arylene group, an alkylenearylenealkylene group, an alkylsilylene group or an alkylgermylene group.) (In the formula (12), R ³⁶ and R ³⁷ are each independently an alkylene group, an aralkylene group, an arylene group, an alkylenearylenealkylene group, an alkylsilylene group or an alkylgermylene group.). The composition according to claim 6, which contains at least one compound having a structure of at least one selected from the group. 8. The stabilizer (D) is an amino compound, an epoxy compound, a thiirane compound, an oxetane compound, an alkoxymethylated melamine compound, an alkoxymethylated glycoluril compound, an alkoxymethylated benzoguanamine compound, an alkoxymethylated urea compound, or an isocyanate. The composition according to claim 1, which is at least one selected from the group consisting of a compound, a cyanate compound, an oxazoline compound, an oxazine compound, and a silyl compound. 9. A composition according to claim 1, which comprises (D) a stabilizer and further comprises a catalyst for the reaction of the (A) degradable compound with the (D) stabilizer. 10. A refractive index lower than that of the decomposable compound (A) selected from the group consisting of (A) decomposable compound, (B) ladder-type polysilsesquioxane, its hydrolyzate and its condensate. The radiation-sensitive refractive index changing composition containing a non-degradable compound, (C) radiation-sensitive decomposing agent and (D) stabilizer is irradiated with radiation and then heated to stabilize the unexposed portion of the stabilizer ( A method for forming a refractive index pattern, which comprises reacting D) with a decomposable compound (A). 11. A refractive index lower than that of the decomposable compound (A) selected from the group consisting of (A) decomposable compound, (B) ladder-type polysilsesquioxane, its hydrolyzate and its condensate. The refractive index changing composition containing the non-decomposable compound and the radiation-sensitive decomposing agent (C) is irradiated with radiation through a pattern mask, and then treated with a stabilizer (D) to form an unexposed portion (A). A method for forming a refractive index pattern, which comprises reacting a decomposable compound with a stabilizer (D). 12. A refractive index lower than that of the decomposable compound (A) selected from the group consisting of (A) decomposable compound, (B) ladder-type polysilsesquioxane, its hydrolyzate and its condensate. After irradiating the refractive index changing composition containing the non-decomposable compound and the radiation-sensitive decomposing agent (C) through a pattern mask, heat treatment is performed to decompose the decomposable polymer in the unexposed area. A characteristic refractive index pattern forming method. 13. The refractive index pattern produced has or does not have voids in the exposed portion.
11. The method according to 11 or 12. 14. A refractive index pattern formed by the method according to claim 10, 11, 12, or 13. 15. The refractive index according to claim 14, which comprises a first region with or without voids and a second region without voids and having a higher refractive index than the first region. pattern. 16. The refractive index pattern according to claim 15, wherein the first region has a smaller elastic modulus than the second region. 17. An optical material having a refractive index pattern formed by the method according to claim 10, 11, 12, or 13.