RU2239859C2 - Composition sensitive to radiation with varying refraction coefficient and method for altering refraction coefficient - Google Patents

Abstract

FIELD: optics.

SUBSTANCE: composition has compound A dissolved by acid or base, compound B not dissolved by acid or base ad having lower refraction coefficient, than compound A, radiation-sensitive dissolving substance C, generating acid or base, and solvent. Effect from radiation on composition through template or mask leads to dissolution of C and A components in radiated portion, as a result of which a difference in refraction coefficients appears between radiated portion and non-radiated portion, and in such way forming a structure having varying refraction coefficients.

EFFECT: stable structure with distributed refraction coefficient and stable optical material independently of use conditions.

6 cl, 8 tbl, 1 dwg, 66 ex

Description

Field of Invention

The present invention relates to a radiation-sensitive composition with a variable refractive index, a method for forming a structure with a distribution of the refractive index, to a structure with a distribution of the refractive index and to optical material. More specifically, it relates to a new radiation-sensitive composition with a variable refractive index used in the field of optoelectronics and the field of display devices, to a method of forming a structure with a distribution of the refractive index, to a structure with a distribution of the refractive index and to optical material.

State of the art

In a modern society called a “multimedia society”, optically shaped products with a refractive index distribution are widely in demand, each of which consists of areas with different refractive indices. Products include not only optical fibers for transmitting information, but also optical diffraction gratings having periodic changes in the refractive index, optical storage devices on which information is recorded in places (on sites) having different refractive indices, optically coupled elements, such as optical integrated circuits (ICs) having finely dispersed (high-precision) structures with a distribution of the refractive index, optical control elements, optical modulating elements and elements of optical transmission.

Optically molded products with a refractive index distribution are divided into two types: the first has a continuous distribution of the refractive index, it includes GI type optical fibers, i.e. gradient fibers (from the English Gradient Index fiber, hereinafter referred to as “GRIN type” optically molded products), the other has a continuous or discontinuous distribution of the refractive index, and this includes optical diffraction gratings and SI type optical waveguides, i.e. . step fibers (from English Step Index fiber).

GRIN type optically molded products attract a lot of attention as the next generation optically molded products. For example, a GI type optical fiber, the refractive index of which decreases from the central axis of the core of the optical fiber to the periphery according to a parabolic law, makes it possible to transmit a large amount of information. GRIN lenses, the refractive index of which is constantly changing, are used as reading lenses used in copying machines, spherical lenses for patch fibers, or microlenses, using their distinctive features, namely that they have a refractive power even on a flat surface, and that they do not have spherical aberration.

To date, a large number of methods have been proposed for producing the above GRIN type optically molded products. For example, in JP-A 9-133813, JP-A 8-336911, JP-A 8-337609, JP-A3-192310, JP-A5-60931 (the term “JP-A”, as used in the present description, means Japanese patent application published without examination ”), WO93 / 19505 and WO94 / 04949 describe a method for producing a GI type optical fiber by dispersing low molecular weight compounds or a monomer in a polymer and continuously distributing its concentration. JP-A 62-25705 describes that a rod-shaped optically molded product or a GI type optical fiber is obtained by photopolymerization of two or more vinyl monomers having different diffraction indices and reactivities (copolymerization reaction constants). In addition, JP-A7-56026 describes a method for obtaining a refractive index distribution by forming polymer A having a photoreactive functional group, dispersing compound B having a lower refractive index than polymer A in polymer A to form a concentration distribution of compound B and photo-interaction polymer A with compound B.

Also proposed are several methods for producing optically molded GRIN type products from inorganic materials. One of them, for example, is a method of producing a GI type rod by adding thallium having a high refractive index to a rod-shaped glass consisting essentially of silicon or lead, immersing the glass in a molten solution containing potassium with a low refractive index, and forming a concentration potassium distribution due to ion exchange.

GRIN lenses can be obtained in a similar manner by applying the above method to a short rod, i.e. a lens-like optical molded product. Alternatively, the GI-type rod obtained by the above method can be cut into layers.

As one of the methods for producing an optically molded product having a finely dispersed (high-precision) structure with a refractive index distribution, such as the above optical diffraction gratings or optical ICs, a technique is known for producing a change in the refractive index by inducing a photochemical reaction in the molded product by irradiation with light. For example, in the case of an inorganic material, glass with an admixture of germanium is irradiated with light, changing its refractive index, to obtain an optical diffraction grating. In the case of organic material, the above technology is known as photochromic reaction or photobleaching, and JP-A7-92313 describes a technology for producing an optical diffraction grating, in which a change in the refractive index is caused by irradiating a laser beam with a material containing low molecular weight compounds dispersed in a polymer and having photochemical reactivity. In addition, JP-A 9-178901 recently proposed the use of this technology to produce a GRIN type optically molded product. This method provides a continuous distribution of the refractive index in the direction inward from the radiation due to the fact that the light emitted on the molded product is absorbed and attenuates its intensity.

However, in the distributions of the refractive index obtained using the above conventional materials, the maximum difference in the refractive index is from about 0.001 to 0.02, and it is difficult to provide a wider distribution of the refractive index to prevent optical loss and suppress malfunction of the circuit.

In the event that the above conventional materials are used under conditions when, after forming the distribution of the refractive index, light passes through them having a wavelength close to the wavelength used to change the refractive index, it is impossible to prevent a phenomenon such as the appearance of a gradual change in the refractive index degrading materials.

SUMMARY OF THE INVENTION

The present invention has been completed in view of the above problems of the prior art.

Thus, it is an object of the present invention to provide an irradiation-sensitive composition with a variable refractive index, the refractive index of the materials of which is changed using a simple method, the difference in refractive indices of which is large enough, and which can provide a stable structure with a distribution of the refractive index and a stable optical material regardless of the conditions of use.

Another objective of the present invention is the development of a radiation-sensitive composition with a variable refractive index, which forms small pores when exposed to radiation, keeps the small pores formed stable and provides a structure with a refractive index distribution having high film strength despite the large number of small since

Another objective of the present invention is to develop a method of forming a structure with a distribution of the refractive index of the above composition of the present invention.

An additional objective of the present invention is to provide a structure with a distribution of the refractive index or optical material obtained by the above method of the present invention.

Other objectives and advantages of the present invention will be apparent from the following description.

Means of solving the problem

Firstly, according to the present invention, the above objectives and advantages of the present invention are achieved using a radiation-sensitive composition with a variable refractive index containing a decomposable acid or base compound (A), not decomposable acid or base compound (B) having a lower refractive index than said acid or base decomposable compound (A), a radiation sensitive decomposing substance (C) generating an acid or base, and a solvent.

Secondly, the above objectives and advantages of the present invention are achieved using the method of forming a structure with a distribution of the refractive index, consisting of regions with different refractive indices, in which a radiation-sensitive composition with a variable refractive index containing decomposable acid or base compound (A), an acid or base non-degradable compound (B), a radiation sensitive decomposing substance (C) generating an acid or base, and a stabilizer (D), subjected to irradiation and heated to react the stabilizer (D) with a degradable acid or base by the compound (A) of the non-irradiated portion.

Thirdly, the above objectives and advantages of the present invention are achieved by a method of forming a structure with a distribution of refractive index, consisting of regions with different refractive indices, in which the composition with a variable refractive index containing decomposable acid or base compound (A), not degradable by acid or a base compound (B) having a lower refractive index than said decomposable acid or base compound (A), and is sensitive to According to the study, the decomposing substance (C) generating an acid or base is irradiated through a template (mask) of the structure and treated with a stabilizer (D) to react the decomposable acid or base of compound (A) in the non-irradiated part with a stabilizer (D).

Fourth, the above objectives and advantages of the present invention are achieved by a method of forming a structure with a distribution of refractive index, consisting of regions with different refractive indices, in which the composition with a variable refractive index containing decomposable acid or base compound (A), not degradable by acid or a base compound (B) having a lower refractive index than said decomposable acid or base compound (A), and sensitive to and To irradiation, the decomposing substance (C) generating an acid or base is irradiated through a template of the structure and heated to decompose the non-irradiated portion decomposed by the acid or base of the polymer.

Fifth, the above objectives and advantages of the present invention are achieved using a structure with a refractive index distribution formed (obtained) by any of the above methods of forming a structure with a distribution of refractive index.

Sixth, the above objectives and advantages of the present invention are achieved using an optical material obtained (formed) by any of the above methods of forming a structure with a distribution of the refractive index.

In a preferred embodiment, the refractive index distribution structure consists of a first region having or not having any pores and a second region having a higher refractive index than the first region and having no pores.

Brief description of the attached drawings

Figure 1 shows a schematic diagram of a device for irradiating light to obtain a lens from a composition with a variable refractive index of the present invention; and

Figure 2 shows a schematic diagram of a device for irradiating light to obtain a diffraction grating from a composition with a variable refractive index of the present invention.

Preferred Embodiments

In the present invention, the term “structure with a refractive index distribution” means a material with a distribution of refractive index, consisting of regions having different refractive indices.

The following is a detailed description of each component of a material with a variable refractive index used in the method of forming a structure with a distribution of the refractive index of the present invention.

Degradable Compound (A)

The decomposable compound (A) used in the present invention can be an acid decomposable compound or a base decomposable compound, and its refractive index is preferably from 1.5 to 1.9. The weight average molecular weight of the decomposable compound (A) is preferably from 100 to 500000, more preferably from 100 to 300000.

The acid degradable compound is selected from compounds having at least one structure selected from the group consisting of structures represented by the following formulas (1) to (8). These compounds can be used individually or as a combination of two or more.

(In the formula (1), R ¹ represents an alkylene group, an alkylene-arylene-alkylene group or an arylene group, and R ² represents an alkylene group, an alkylene-arylene-alkylene group, an arylene group, an alkylsilylene group or an alkyl germylene group).

(In the formula (2), M represents Si or Ge, R ³ represents an alkylene group, an alkylene-arylene-alkylene group, an arylene group, an alkylsilylene group or an alkyl-germylene group, R ⁴ represents an oxygen atom, an alkylene group, an alkylene-arylene- an alkylene group, an arylene group or a single bond, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a thioalkyl group, and m is an integer from 0 to 2 )

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

(In formula (4), R ¹¹ represents an oxyalkylene group or a single bond, and R ¹² represents a hydrogen atom, an alkyl group, an alkylene-arylene-alkylene group or an aryl group.)

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

(In the formula (6), R ¹⁴ represents an alkylene group or structure represented by the following formulas (6) -1, (6) -2 or (6) -3:

(In the formula (6) -1 R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, a chain alkyl group containing from 1 to 6 carbon atoms, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl a group, a mercapto group, a carboxyl group, an alkoxyl group containing from 1 to 6 carbon atoms, an alkylthio group containing from 1 to 6 carbon atoms, a haloalkyl group containing from 1 to 6 carbon atoms, a haloalkoxy group containing from 1 to 6 carbon atoms, haloalkylthio group containing from 1 to 6 carbon atoms, hydro a sialkyl group containing from 1 to 6 carbon atoms, a mercaptoalkyl group containing from 1 to 6 carbon atoms, a hydroxyalkoxy group containing from 1 to 6 carbon atoms, a mercaptoalkylthio group containing from 1 to 6 carbon atoms, an aryl group containing from 6 to 10 carbon atoms or an aralkyl group containing from 7 to 11 carbon atoms.)

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

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

(In formula (7), R ²¹ represents an alkylene group, an alkylene-arylene-alkylene group or an arylene group.)

where R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a chain alkyl group containing from 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 containing from 1 to 6 carbon atoms, an alkylthio group containing from 1 to 6 carbon atoms, a haloalkyl group containing from 1 to 6 carbon atoms, a haloalkoxyl group containing from 1 to 6 carbon atoms, a haloalkyl group containing from 1 to 6 carbon atoms, hydroxyalkyl a group containing from 1 to 6 carbon atoms, a mercaptoalkyl group containing from 1 to 6 carbon atoms, a hydroxyalkoxy group containing from 1 to 6 carbon atoms, a mercaptoalkylthio group containing from 1 to 6 carbon atoms, an aryl group containing from 6 up to 10 carbon atoms, or an aralkyl group containing from 7 to 11 carbon atoms.

The base degradable compound is selected from compounds having at least one structure selected from the group consisting of structures represented by the following formulas (9) to (12). These compounds can be used individually or as a combination of two or more.

(In formula (9), R ²⁶ represents an alkylene group, an aralkylene group or an arylene group, R ²⁷ represents an alkylene group, an aralkylene group, an arylene group, an alkylene-arylene-alkylene group, an alkylsilylene group or an alkyl germylene group, R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or a thioalkyl group, and i and j, each independently, are 0 or 1,

(In formula (10), R ³² represents an alkylene group, an aralkylene group or an arylene group, and R ³³ represents an alkylene group, an aralkylene group, an arylene group, an alkylene-arylene-alkylene group, an alkylsilylene group, or an alkylherylene group.)

(In formula (11), R ³⁴ and R ³⁵ each independently represent an alkylene group, an aralkylene group, an arylene group, an alkylene-arylene-alkylene group, an alkylsilylene group, or an alkyl germylene group.)

(In formula (12), R ³⁶ and R ³⁷ each independently represent an alkylene group, an aralkylene group, an arylene group, an alkylene-arylene-alkylene group, an alkylsilylene group, or an alkyl germylene group.)

All of the above alkylene-arylene-alkylene groups, each independently, have a structure represented by the following formulas (13) or (14):

(In formula (13), R ³⁸ , R ³⁹ , R ^40, and R ⁴¹ each independently represent a hydrogen atom, a chain alkyl group containing from 1 to 6 carbon atoms, or an aryl group containing from 6 to 10 carbon atoms, and R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ each independently represent a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxyl group, a thioalkyl group, an alkyl ester group, an alkylthio ester group, an aryl group, a cyano group or nitro group)

(In formula (14), R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ each independently represent a hydrogen atom, a chain alkyl group containing from 1 to 6 carbon atoms, or an aryl group containing from 6 to 10 carbon atoms, R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxyl group, a thioalkyl group, an alkyl ester group, alkylthio ester group, aryl group, cyano group or nitro group, And ¹ represents –S-, -O-, -SO ₂ -, -CO-, -COO-, -OSOO-,

-CH ₂ - or-C (R ⁵⁸ ) ₂ -, and R ⁵⁸ represents a chain alkyl group containing from 1 to 6 carbon atoms.)

All of the above arylene groups, each independently, have a structure represented by the following formula (15):

where everything from R ⁵⁹ to R ⁶⁶ , each independently, is 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 alkylthio ester group, an aryl group, a cyano group or a nitro group, A ² represents -S-, -O-, -SO ₂ -, -CO-, -COO-,

-OSOO-, -CH ₂ - or -C (R ⁶⁷ ) ₂ -, and R ⁶⁷ is a chain alkyl group containing from 1 to 6 carbon atoms).

All of the above alkylsilylene groups, each independently, have a structure represented by the following formula (16):

where R ⁶⁸ , R ⁶⁹ , R ⁷⁰ and R ⁷¹ each independently represent a hydrogen atom, a chain alkyl group containing from 1 to 6 carbon atoms, or an aryl group containing from 6 to 10 carbon atoms, And ³ represents - O-, alkylene group or arylene group, and a is an integer equal to 0 or 1.

All of the above alkyl germylene groups, each independently, have a structure represented by the following formula (17):

where R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ each independently represent a hydrogen atom, a chain alkyl group containing from 1 to 6 carbon atoms, or an aryl group containing from 6 to 10 carbon atoms, And ⁴ represents - O-, alkylene group or an arylene group, and b is an integer equal to 0 or 1.

Preferably, the alkylene groups in the above formulas (16) and (17), each independently, are a linear, branched or cyclic alkylene group containing from 1 to 10 carbon atoms, such as methylene, 1,2-ethylene, 1,3-trimethylene or 1,10-decamethylene, and the hydrogen atoms in the above groups may be substituted, for example, with a chlorine atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxyl group, a thioalkyl group, an alkyl ester group, an alkylthio ester group, an aryl group or cyan group.

Preferably, the alkyl groups in all of the above alkyl groups, alkoxyl groups, thioalkyl groups, alkyl ester groups and alkylthio ester groups, each independently, are a linear, branched or cyclic alkyl group containing from 1 to 10 carbon atoms and hydrogen atoms in the above groups can be replaced by a chlorine atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxyl group, a thioalkyl group, an alkyl ester group, an alkylthio complex oefirnoy group, an aryl group or a cyano group.

All of the above aryl groups, each independently, are a phenyl group, a naphthyl group, an anthracenyl group or a biphenyl group, and the hydrogen atoms in the above groups can be replaced by a chlorine atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxyl group, a thioalkyl group, an alkyl ester a group, an alkylthio ester group, a cyano group or a nitro group.

The alkyl chain group containing from 1 to 6 carbon atoms in the above formulas (6) -1 and (8) may be linear or branched, as illustrated by examples, methyl, ethyl, n-propyl, iso-propyl, n- butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl and n-hexyl.

The alkoxy group containing from 1 to 6 carbon atoms may be linear or branched, for example, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy neopentyloxy, n-hexyloxy and thhexyloxy group.

An alkylthio group having from 1 to 6 carbon atoms may be linear or branched, for example methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio , neopentylthio, n-hexylthio and tert-hexylthio group.

Examples of a haloalkyl group containing from 1 to 6 carbon atoms include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, chloromethyl, 2-chloroethyl, 3-chloropropyl,

1-chloromethylethyl, 4-chlorobutyl, 2-chloromethylpropyl,

5-chloropentyl, 3-chloromethylbutyl, 2-chloroethylpropyl,

6-chlorhexyl, 3-chloromethylpentyl, 4-chloromethylpentyl,

2-chloroethyl butyl, bromomethyl, 2-bromoethyl, 3-bromopropyl,

1-bromomethylethyl, 4-bromobutyl, 2-bromomethylpropyl,

5-bromopentyl, 3-bromomethylbutyl, 2-bromoethylpropyl,

6-bromohexyl, 3-bromomethylpentyl, 4-bromomethylpentyl and

2-bromoethyl butyl.

Examples of a haloalkoxy group containing from 1 to 6 carbon atoms include trifluoromethoxy, pentafluoroethoxy, heptafluoropropoxy, chloromethoxy,

2-chloroethoxy, 3-chloropropoxy, 1-chloromethylethoxy,

4-chlorobutoxy, 2-chloromethylpropoxy, 5-chloropentyloxy,

3-chloromethylbutoxy, 2-chloroethylpropoxy, 6-chlorohexyloxy,

3-chloromethylpentyloxy, 4-chloromethylpentyloxy,

2-chloroethylbutoxy, bromomethoxy, 2-bromoethoxy, 3-bromopropoxy, 1-bromomethylethoxy, 4-bromobutoxy, 2-bromomethylpropoxy,

5-bromopentyloxy, 3-bromomethylbutoxy, 2-bromoethylpropoxy,

6-bromohexyloxy, 3-bromomethylpentyloxy,

4-bromomethylpentyloxy and 2-bromoethylbutoxy groups.

Examples of a haloalkylthio group containing from 1 to 6 carbon atoms include trifluoromethylthio, pentafluoroethylthio, heptafluoropropylthio, chloromethylthio,

2-chloroethylthio, 3-chloropropylthio, 1-chloromethylethylthio,

4-chlorobutylthio, 2-chloromethylpropylthio, 5-chloropentylthio,

3-chloromethylbutylthio, 2-chloroethylpropylthio, 6-chlorhexylthio,

3-chloromethylpentylthio, 4-chloromethylpentylthio,

2-chloroethyl butylthio, bromomethylthio, 2-bromoethylthio,

3-bromopropylthio, 1-bromomethylethylthio, 4-bromobutylthio,

2-bromomethylpropylthio, 5-bromopentylthio, 3-bromomethylbutylthio, 2-bromoethylpropylthio, 6-bromohexylthio, 3-bromomethylpentylthio, 4-bromomethylpentylthio and 2-bromoethylbutylthio groups.

Examples of a hydroxyalkyl group containing from 1 to 6 carbon atoms include hydroxymethyl,

2-hydroxyethyl, 3-hydroxypropyl, 1-hydroxymethylethyl,

4-hydroxybutyl, 2-hydroxymethylpropyl, 5-hydroxypentyl,

3-hydroxymethylbutyl, 2-hydroxyethylpropyl, 6-hydroxyhexyl, 3-hydroxymethylpentyl, 4-hydroxymethylpentyl and

2-hydroxyethyl butyl.

Examples of a mercaptoalkyl group containing from 1 to 6 carbon atoms include mercaptomethyl,

2-mercaptoethyl, 3-mercaptopropyl, 1-mercaptomethylethyl,

4-mercaptobutyl, 2-mercaptomethylpropyl, 5-mercaptopentyl,

3-mercaptomethylbutyl, 2-mercaptoethylpropyl, 6-mercaptohexyl, 3-mercaptomethylpentyl, 4-mercaptomethylpentyl and

2-mercaptoethyl butyl.

Examples of a hydroxyalkoxy group containing from 1 to 6 carbon atoms include hydroxymethoxy,

2-hydroxyethoxy, 3-hydroxypropoxy, 1-hydroxymethylethoxy, 4-hydroxybutoxy, 2-hydroxymethylpropoxy,

5-hydroxypentyloxy, 3-hydroxymethylbutoxy,

2-hydroxyethylpropoxy, 6-hydroxyhexyloxy,

3-hydroxymethylpentyloxy, 4-hydroxymethylpentyloxy and

2-hydroxyethylbutoxy groups.

Examples of a mercaptoalkylthio group containing from 1 to 6 carbon atoms include mercaptomethylthio,

2-mercaptoethylthio, 3-mercaptopropylthio,

1-mercaptomethylethylthio, 4-mercaptobutylthio,

2-mercaptomethylpropylthio, 5-mercaptopentylthio,

3-mercaptomethylbutylthio, 2-mercaptoethylpropylthio,

6-mercaptohexylthio, 3-mercaptomethylpentylthio,

4-mercaptomethylpentylthio and 2-mercaptoethylbutylthio groups.

Examples of the aryl group containing from 6 to 10 carbon atoms include phenyl, tolyl, xylyl, cumenyl and

1-naphthyl.

Examples of an aralkyl group containing from 7 to 11 carbon atoms include benzyl, α-methylbenzyl, phenethyl and naphthylmethyl.

Methods for preparing acid-degradable compounds having the structures represented in the present invention by the above formulas (1) to (7), for example, as a repeating unit, are already known.

Methods of preparing a compound having the structure represented by the above formula (1) are described in Polymer Bull., 1, 199 (1978), JP-A 62-136638, EP 225454, US 806597, JP-A 4-303843, JP-A 7-56354 etc.

Methods of preparing a compound having the structure represented by the above formula (2) are described in Macromolecules 29, 5529 (1996), Polymer 17, 1086 (1976), JP-A 60-37549, etc.

Methods for preparing a compound having the structure represented by the above formula (3) are described in Electrochem. Soc., Solid State Sci. Technol., 133 (1) 181 (1986), J. Imaging Sci., 30 (2) 59 (1986), Macromol. Chem., Rapid Commun., 7, 121 (1986), etc.

Methods for preparing a compound having the structure represented by the above formula (4) are described in US Pat. No. 3,894,253, Japanese Patents JP-A 62-190211, JP-A2-146544, Macromol. Chem., 23, 16 (1957), JP-A 63-97945, Polymer Sci., A-1, 8, 2375 (1970), US Pat. No. 4,247,611, EP 41657, JP-A 57-31674, JP-A 64 -3647, JP-A 56-17345, etc.

Methods for preparing a compound having the structure represented by the above formula (5) are described in Prepr.Eur.DiscMeet.Polymer Sci., Strasbourg, p.106 (1978), Macromol. Chem., 179, 1689 (1978), etc.

Methods of preparing a compound having the structure represented by the above formula (6) are described in US Pat. No. 3,894,253, US Pat. No. 3,940,507, Japanese Patent JP-A 62-190211, etc.

Methods of preparing a compound having the structure represented by the above formula (7) are described in J. Am. Chem. Soc., 54, 1579 (1932), J. Polym. Sci., 29, 343 (1958), J. Polymer Sci ., Part A, Polym. Chem., 25, 3373 (1958), Macromolecules, 25, 12, (1992), Macromolecules, 20, 705, (1997), Macromolecules, 21, 1925, (1998), Macromol.Chem ., Rapid. Commun., 11, 83 (1990), etc.

A compound having the structure represented by the above formula (8) can be prepared by cationic or anionic polymerization of a compound represented by the following formula (8) -1 in a solvent in the presence of, if necessary, a molecular weight modifier:

where R ²⁰¹ , R ²⁰² , R ²⁰³ and R ²⁰⁴ each independently represent a group selected from the group represented by R ²² , R ²³ , R ²⁴ and R ²⁵ in the formula (8).

A compound represented by the above formula (8) may be a copolymer of one or more compounds selected from the group consisting of a compound represented by the following formula (8) -2, a compound represented by the following formula (8) -3 and a monomer other than them, and the compounds represented by the above formula (8) -1. In this case, the total amount of one or more compounds selected from the group consisting of the compound represented by the following formula (8) -2, the compound represented by the following formula (8) -3 and a monomer different from them may be 100 parts or less by weight based on 100 parts by weight of the compound represented by the above formula (8) -1.

where R ²⁰⁵ represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms, and R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ and R ²¹⁰ each independently represent a hydrogen atom, a chain alkyl group containing from 1 up to 6 carbon atoms, chlorine atom, bromine atom, iodine atom, hydroxyl group, mercapto group, carboxyl group, alkoxyl group containing from 1 to 6 carbon atoms, alkylthio group containing from 1 to 6 carbon atoms, halogen-alkyl group containing from 1 to 6 carbon atoms, halogenated, containing having from 1 to 6 carbon atoms, a haloalkylthio group containing from 1 to 6 atoms, a hydroxyalkyl group containing from 1 to 6 carbon atoms, a mercaptoalkyl group containing from 1 to 6 carbon atoms, a hydroxyalkoxy group containing from 1 to 6 atoms carbon, mercaptoalkylthio group containing from 1 to 6 carbon atoms, an aryl group containing from 6 to 10 carbon atoms, or an aralkyl group containing from 7 to 11 carbon atoms, or two of R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ and R ²¹⁰ can be linked together to form a 4-7 membered ring e with the carbon atoms with which they are associated,

where R ²¹¹ and R ²¹² each independently represent a hydrogen atom, an alkyl group containing from 1 to 10 carbon atoms, a haloalkyl group containing from 1 to 10 carbon atoms, a hydroxyalkyl group containing from 1 to 10 carbon atoms, a mercaptoalkyl group containing from 1 to 10 carbon atoms, an aryl group containing from 6 to 10 carbon atoms, an aralkyl group containing from 7 to 11 carbon atoms, (polyethylene glycol) ethyl group containing 1-5 ethyleneoxy repeating units,

(polypropylene glycol) propyl group containing 1-5 propyleneoxy repeating units, (polyethylene sulfide) ethyl group containing 1-5 repeating units, or (polypropylene sulfide) propyl group containing 1-5 repeating units.

Examples of monomers that differ from the data include compounds having two aldehyde groups in one molecule, such as glyoxal, succinic aldehyde, glutaraldehyde, maleic aldehyde, 1,8-octanedialdehyde,

m-phthalaldehyde, p-phthalaldehyde,

2,3-naphthalenedicarboxaldehyde, 2,3-anthracene dicarboxaldehyde, 9,10-anthracene dicarboxaldehyde, 4,4'-bisbenzaldehyde,

2,5-dimethoxy-1,4-dicarboxaldehyde,

2,2 ’- (ethylenedioxy) dibenzaldehyde,

2,2’-bisphenyldicarboxaldehyde, bis (2-formylphenyl)

ether and 6,6’-dihydroxy-5,5’-dimethoxy- [1,1’-biphenyl] -3,3’-dicarboxaldehyde; and compounds having three or more aldehyde groups in one molecule, such as a chromium complex with salicylic aldehyde, aluminum formyl acetate, (1,1 ', 3', 1 '') - terphenyl-2,6,2 '', 6 '' tetracarbaldehyde,

2-hydroxybenzene-1,3,5-tricarbaldehyde and

1,2,4,5-tetra (p-formylphenyl) benzene.

You can also use the compounds obtained by replacing the hydrogen atoms in the above compounds with an alkoxyl group containing from 1 to 10 carbon atoms, a halogenated group containing from 1 to 10 carbon atoms, a halogenated group containing from 1 to 10 carbon atoms, halogenated alkyl group, containing from 1 to 10 carbon atoms, a hydroxyalkyl group containing from 1 to 10 carbon atoms, a mercaptoalkyl group containing from 1 to 10 carbon atoms, a hydroxyalkoxy group containing from 1 to 10 carbon atoms kind, mercaptoalkylthio group containing from 1 to 10 carbon atoms, an aryl group containing from 6 to 10 carbon atoms, an aralkyl group containing from 7 to 11 carbon atoms, (polyethylene glycol) ethyl group containing 1-5 repeating units or (polypropylene glycol ) a propyl group containing 1-5 repeating units.

Cationic polymerization and / or anionic polymerization to obtain a compound having the structure represented by the above formula (8) can be carried out in the presence of an anionic polymerization catalyst, a coordinating anionic polymerization catalyst or a cationic polymerization catalyst. Typical examples of an anionic polymerization catalyst or a coordinating anionic polymerization catalyst include alkali metals such as sodium or lithium, alkali metal compounds such as sec-butyl lithium; alkali metal complexes such as sodium / naphthalene; alkali metal alkoxides such as sodium methoxide; amines such as

n-butylamine and diethylamine; quaternary ammonium salts such as ammonium stearate and tetrabutylammonium acetate; and tetravalent tin organic compounds such as dibutyltin dilaurate, tributyltin chloride and dilaurate diethyltin.

Typical examples of cationic polymerization catalysts include tin tetrachloride, tin tetrabromide, titanium tetrachloride, aluminum trichloride, zinc chloride, boron trifluoride, boron trifluoride diethyl etherate, perchloric acid, acetyl perchlorate, p-toluenesulfonic acid, triethyltinium trifluoronium triethloronitride, trifluoronethyltin ethyl trifluoronium trisulfonium trifluoronethyltin ethyl trifluoronium trifluoronium trisulfonate.

Examples of a solvent for polymerization include aliphatic hydrocarbons such as hexane, heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic halogenated hydrocarbons such as methylene chloride, ethylene chloride and carbon tetrachloride; and aromatic halogenated hydrocarbons such as chlorobenzene and ortho-dichlorobenzene. These organic solvents may be used individually or as a mixture of two or more thereof. The organic solvent is preferably dehydrated and completely purified.

The molecular weight modifier that may be present in the preparation of the polymer is preferably uniformly dissolved or dispersed in the reaction system, and alcohol or carboxylic acid can be used as the molecular weight modifier.

Examples of the alcohol include methyl alcohol, ethyl alcohol, hexyl alcohol, cyclohexyl alcohol and benzyl alcohol. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, lauric acid, palmitic acid and benzoic acid. The amount of molecular weight modifier is suitably adjusted according to the molecular weight of the desired polymer, and it can easily be determined experimentally.

The reaction temperature is preferably set in the range from -200 to 50 ° C. However, taking into account the freezing point and boiling point of the organic solvent, it is more preferable in most cases to use a range from -100 to 30 ° C. The reaction time is not particularly limited, but can be set appropriately in the range of 100 hours or less. After passing a predetermined polymerization time, for example, the resulting reaction mixture is filtered and the resulting solid is washed with ion-exchanged water and dried in vacuum, obtaining the target compound having the structure represented by the above formula (8). Since the hydroxyl group at the end of the semi-acetal type molecule formed during the above polymerization reaction has a certain lack of thermal stability, it is closed at the end of the molecule using a method known as a means of closing the semi-acetal-based polymer, such as esterification, esterification with ether formation or urethaneation, depending on what is needed to improve its stability.

Also known are methods of preparing base decomposable compounds having, as repeating units, the structures represented by the above formulas (9) to (12).

Methods for preparing a compound having the structure represented by the above formula (9) are described in Macromol. Chem., Rapid Commun., 5, 151 (1984), Macromol. Chem., 189, 2229 (1988), Macromol. Chem., 187, 2525 (1986), Polym. J., 22, 803 (1990), etc.

Methods of preparing a compound having the structure represented by the above formula (10) are described in J. Polym. Sci., 47, 1523 (1993), J. Appl. Polym.Sci., 35, 85 (1985), J. Polym. Sci., Polym. Chem. Ed., 22, 1579 (1984), J. Polym. Sci., Polym. Chem. Ed., 14, 655 (1976), J. Polym. Sci., Polym. Chem. Ed ., 17, 2429 (1979), etc.

Methods of preparing a compound having the structure represented by the above formula (11) are described in J. Macromol.Sci.Chem., A9, 1265 (1975), etc.

Methods for preparing a compound having the structure represented by the above formula (12) are described in Polym. Bull., 14, 85 (1985), Macromol. Chem., 189, 1323 (1988), etc.

Non-degradable compound (B)

The non-degradable compound (B) used in the present invention is stable to acid or base and preferably has high optical permeability (transparency). The refractive index of component (B) can be set appropriately and adjusted to a preferred value according to the purpose of the application. The refractive index n _{B of the} compound (B) is less than the refractive index n _{A of} polymer A and, particularly preferably, satisfies the following expression (1).

The non-degradable compound (B) may be an indecomposable polymer.

Examples of non-degradable polymer (B) include an acrylic resin, a urethane resin, a polyester resin, a polycarbonate resin, a norbornene resin, a styrene resin, a polyethersulfone resin, a silicone resin, a polyamide resin, a polyimide resin, a polysiloxane-based resin, a fluorinated resin, a polybutadiene-based resin, a vinyl ether-based resin, and a vinyl ester-based resin. A preferred non-degradable polymer (B) may be suitably selected according to the refractive index of the degradable polymer (A) used. In order to increase the difference between the refractive index of the degradable polymer (A) and the refractive index of the degradable polymer (B) and to reduce the loss of optical permeability if the optical path is long, it is preferable to use an indecomposable polymer (B) having a fluorine atom replacing the hydrogen atom in the above resin.

Illustrative examples of non-degradable polymer (B) include the following polymers (the numbers in parentheses are refractive index values measured using the d-ray): polyvinylidene fluoride (1.42), polydimethylsiloxane (1.43), polytrifluoroethyl methacrylate (1.44) , polyoxypropylene (1.45), polyvinyl isobutyl ether (1.45), polyvinyl ethyl ether (1.45), polyoxyethylene (1.46), polyvinyl butyl ether (1.46), polyvinyl pentyl ether (1.46) , polyvinyl hexyl ether (1.46), poly (4-methyl-1-pentene) (1.46 to 1.47), butyrate ac cellulose acetate (1.46 to 1.49)

poly (4-fluoro-2-trifluoromethylstyrene) (1.46),

polyvinyl octyl ether (1.46),

poly (vinyl-2-ethylhexyl ether) (1.46),

polyvinyl decyl ether (1.46),

poly (2-methoxyethyl acrylate) (1.46), polybutyl acrylate (1.46), polybutyl acrylate (1.47), poly (tert-butyl methacrylate) (1.46), polyvinyl dodecyl ether (1.46),

poly (3-ethoxypropyl acrylate) (1.47),

polyoxycarbonyltetramethylene (1.47),

polyvinyl propionate (1.47), polyvinyl acetate (1.47),

polyvinyl methyl ether (1.47),

polyethyl acetate (1.47), ethylene-vinyl acetate copolymer (1.47 to 1.50), cellulose propionate (80% to 20% vinyl acetate) (1.47 to 1.49), cellulose acetate propionate (1.47) benzyl cellulose (1.47 to 1.58), phenol-formaldehyde resin (1.47 to 1.70), cellulose triacetate (1.47 to 1.48), polyvinyl methyl ether (isotactic) (1.47),

poly (3-methoxypropyl acrylate) (1.47),

poly (2-ethoxyethyl acrylate) (1.47),

polymethyl acrylate (1.47-1.48), polyisopropyl methacrylate (1.47), poly (1-decene) (1.47), polypropylene (atactic, density 0.8575 g / cm ³ ) (1.47), poly (vinyl sec-butyl ether) (isotactic) (1.47), polydodecylmethacrylate (1.47),

polyoxyethyleneoxy succinoyl (1.47),

(polyethylene succinate) polytetradecylmethacrylate (1.47),

ethylene-propylene copolymer (EPR-rubber) (1.47-1.48),

polyhexadecyl methacrylate (1.48), polyvinyl formate (1.48), poly (2-fluoroethyl methacrylate) (1.48),

polyisobutyl methacrylate (1.48), ethyl cellulose (1.48),

polyvinyl acetal (1.48 to 1.50),

cellulose acetate (1.48 to 1.50), cellulose tripropionate (1.48 to 1.49), polyoxymethylene (1.48), polyvinyl butyral (1.48 to 1.49), poly (n-hexylmethacrylate) (1 , 48),

poly (n-butyl methacrylate) (1.48), polyethylidene dimethacrylate (1.48),

poly (2-epoxyethyl methacrylate) (1.48),

polyoxyethylene oximealeoyl (1.48),

(polyethylene maleate) poly (n-propyl methacrylate) (1.48),

poly (3,3,5-trimethylcyclohexyl methacrylate) (1.49),

polyethyl methacrylate (1.49),

poly (2-nitro-2-methylpropylmethacrylate) (1.49),

polytriethylcarbinylmethacrylate (1.49),

poly (1,1-diethylpropylmethacrylate) (1.49),

polymethyl methacrylate (1.49), poly (2-decyl-1,3-butadiene (1.49), polyvinyl alcohol (1.49 to 1.53), polyethylene glycolate methacrylate (1.49), poly (3-methylcyclohexyl methacrylate) (1.49), poly (cyclohexyl α-ethoxyacrylate) (1.50),

methyl cellulose (low viscosity) (1.50),

poly (4-methylcyclohexyl methacrylate) (1.50),

polydecamethylene glycol dimethacrylate (1.50),

polyurethane (1.50 to 1.60),

poly (1,2-butadiene) (1.50), polyvinyl formal (1.50),

poly (2-bromo-4-trifluoromethylstyrene) (1.50),

cellulose nitrate (1.50 to 1.51),

poly (sec-butyl α-chloroacrylate) (1.50),

poly (2-heptyl-1,3-butadiene) (1.50),

poly (ethyl α-chloroacrylate) (1.50),

poly (2-isopropyl-1,3-butadiene) (1.50),

poly (2-methylcyclohexyl methacrylate) (1.50),

polypropylene (density 0.9075 g / cm ³ ) (1.50),

polyisobutene (1.51), polybornylmethacrylate (1.51),

poly (2-tert-butyl-1,3-butadiene) (1.51),

polyethylene glycol dimethacrylate (1.51),

polycyclohexyl methacrylate (1.51),

poly (cyclohexanediol-1,4-dimethacrylate) (1.51),

butyl rubber (unvulcanized) (1.51),

polytetrahydrofurfuryl methacrylate) (1.51), gutta-percha (β) (1.51), polyethylene ionomer (1.51), polyoxyethylene (high molecular weight) (1.51 to 1.54), polyethylene (density 0.914 g / cm ³ ) (1.51), (density from 0.94 to 0.945 g / cm ³ ) (1.52 to 1.53), (density 0.965 g / cm ³ ) (1.55),

poly (1-methylcyclohexyl methacrylate) (1.51),

poly (2-hydroxyethyl methacrylate) (1.51),

polyvinyl chloroacetate (1.51),

polybutene (isotactic) (1.51),

polyvinyl methacrylate (1.51),

poly (N-butyl methacrylamide) (1.51), gutta-percha (α) (1.51), terpene resin (1.52), poly (1,3-butadiene) (1.52),

shellac (1.51 to 1.53), poly (methyl α-chloroacetate) (1.52), poly (2-chloroethyl methacrylate) (1.52),

poly (2-diethylaminoethyl methacrylate) (1.52),

poly (2-chlorocyclohexyl methacrylate) (1.52),

poly (1,3-butadiene) (35% cis form, 56% trans form 1.5180;

7% form with 1,2-bond), natural rubber (1,52),

polyallyl methacrylate (1.52),

polyvinyl chloride + 40% dioctyl phthalate (1.52),

polyacrylonitrile (1.52), polymethacrylonitrile (1.52),

poly (1,3-butadiene) (enriched in cis type) (1.52),

butadiene-acrylonitrile copolymer (1.52),

polymethylisopropenyl ketone (1.52), polyisoprene (1.52),

hard polyester resin (approximately 50% styrene) (1.52 to 1.54), poly (N- (2-methoxyethyl) methacrylamide) (1.52),

poly (2,3-dimethylbutadiene) (methyl rubber) (1.53),

vinyl chloride-vinyl acetate copolymer (95/5 to 90/10) (1.53 to 1.54), polyacrylic acid (1.53),

(1,3-dichloropropyl methacrylate) (1.53),

poly (2-chloro-1- (chloromethyl) ethyl methacrylate) (1.53),

polyacrolein (1.53), poly (1-vinyl-2-pyrrolidone) (1.53),

hydrochlorinated rubber (1.53 to 1.55), nylon 6; nylon 6.6; nylon 6.10 (cast product) (1.53), styrene-butadiene copolymer (approximately 30% styrene) (1.53), poly (cyclohexyl-α-chloroacrylate) block copolymer (1.53), poly (2-chloroethyl α-chloroacrylate) (1.53), styrene-butadiene copolymer (about 75/25) (1.54), poly (2-aminoethyl methacrylate) (1.54),

polyfurfuryl methacrylate (1.54),

polybutyl mercaptyl methacrylate (1.54),

poly (1-phenyl-n-amylmethacrylate) (1.54),

poly (N-methyl-methacrylamide) (1.54), cellulose (1.54),

polyvinyl chloride (1.54 to 1.55), urea-formaldehyde resin (1.54 to 1.56), poly (sec-butyl α-bromacrylate) (1.54), poly (cyclohexyl α-bromacrylate) (1, 54)

poly (2-bromoethyl methacrylate) (1.54),

polydihydroabietic acid (1.54),

polyiabietic acid (1,546),

polyethyl mercaptyl methacrylate (1.55),

poly (N-allylmethacrylamide) (1.55),

poly (1-phenylethylmethacrylate) (1.55),

polyvinylfuran (1.55), poly (2-vinyltetrahydrofuran) (1.55),

poly (vinyl chloride) + 40% tricresyl phosphate (1.55),

poly (p-methoxybenzyl methacrylate) (1.55),

polyisopropyl methacrylate (1.55),

poly (p-isopropyl styrene) (1.55), polychloropropene (1.55 to 1.55), poly (oxyethylene-α-benzoate-ω-methacrylate) (1.56),

poly (p, p’-xylylene dimethacrylate) (1.56),

poly (1-phenylallylmethacrylate) (1.56),

poly (p-cyclohexylphenylmethacrylate) (1.56),

poly (2-phenylethylmethacrylate) (1.56),

poly (hydroxycarbonyloxy-1,4-phenylene-1-propyl) (1.56),

poly (1- (o-chlorophenyl) ethyl methacrylate) (1.56),

styrene-maleic anhydride copolymer (1.56),

poly (1-phenylcyclohexylmethacrylate) (1.56),

poly (hydroxycarbonyloxy-1,4-phenylene-1,3-dimethyl-butylidene-

1,4-phenylene) (1.57), poly (methyl-α-bromacrylate) (1.57),

polybenzyl methacrylate (1.57),

poly (2- (phenylsulfonyl) ethyl methacrylate) (1.57),

poly (m-cresyl methacrylate) (1.57),

styrene-acrylonitrile copolymer (about 75/25) (1.57),

poly (hydroxycarbonyloxy-1,4-phenylene-isobutylidene-1,4-phenylene)

(1.57), poly (o-methoxyphenylmethacrylate) (1.57),

polyphenyl methacrylate (1.57), poly (o-cresyl methacrylate) (1.57), polydiallyl phthalate (1.57),

poly (2,3-dibromopropylmtacrylate) (1.57),

poly (hydroxycarbonyloxy-1,4-phenylene-1-methyl-butylidene-1,4-phenylene) (1.57), poly (hydroxy-2,6-dimethylphenylene) (1.58),

polyoxyethylene oxyterephthaloyl (amorphous) (1.58), polyethylene terephthalate (1.51 to 1.64), polyvinyl benzoate (1.58), poly (hydroxycarbonyloxy-1,4-phenylenebutylidene-1,4-phenylene) (1,58 ), poly (1,2-diphenylethylmethacrylate) (1.58),

poly (o-chlorobenzyl methacrylate) (1.58), poly (oxycarbonyloxy-1,4-phenylene-sec-butylidene-1,4-phenylene) (1.58),

polyoxypentaerythritoloxyphthaloyl (1.58),

poly (m-nitrobenzylmethacrylate) (1.58), poly (hydroxycarbonyloxy-1,4-phenylene-isopropylidene-1,4-phenylene) (1.59),

poly (N- (2-phenylethyl) methacrylamide) (1.59),

poly (4-methoxy-2-methylstyrene) (1.59),

poly (o-methylstyrene) (1.59), polystyrene (1.59),

poly (hydroxycarbonyloxy-1,4-phenylenecyclohexylidene-1,4-phenylene) (1.59), poly (o-methoxy styrene) (1.59),

polydiphenylmethyl methacrylate (1.59),

poly (hydroxycarbonyloxy-1,4-phenylene-ethylidene-1,4-phenylene) (1.59), poly (p-bromophenylmethacrylate) (1.60),

poly (N-benzyl methacrylamide) (1.60),

poly (p-methoxystyrene) (1.60), polyvinylidene chloride (1.60 to 1.63), polysulfide (“Thiokol”) (1.6 to 1.7),

poly (o-chlorodiphenylmethyl methacrylate) (1.60),

poly (oxycarbonyloxy-1,4- (2,6-dichloro) phenyleneisopropylidene-1,4- (2,6-dichlorophenylene) (1.61), poly (oxycarbonyloxybis (1,4- (3,5-dichlorophenylene)) ) polypentachlorophenylmethacrylate (1.61), poly (o-chlorostyrene) (1.61), poly (phenyl-α-bromacrylate) (1.61), poly (p-divinylbenzene) (1.62), poly (N- vinylphthalimide) (1.62), poly (2,6-dichlorostyrene) (1,62), poly (β-naphthylmethacrylate) (1,63), poly (α-naphthylcarbinylmethacrylate) (1,63), polysulfone (1, 63), poly (2-vinylthiophene) (1.64), poly (α-naphthylmethacrylate) (1.64), poly (hydroxycarbonyloxy-1,4-phenylenediphenylmethylene-1,4-phenylene) (1.65) polyvinyl phenyl sulfide (1.66),

butylphenol formaldehyde resin (1.66),

urea-thiourea-formaldehyde resin (1.66),

polyvinylnaphthalene (1.68), polyvinylcarbazole (1.68),

naphthalene-formaldehyde resin (1.70),

phenol-formaldehyde resin (1.70),

polypentabromophenylmethacrylate (1.71), etc.

Among them, compounds having a d-ray refractive index of 1.6 or less are preferred and compounds having a d-ray refractive index of 1.5 or less are more preferred.

The weight average molecular weight of the non-degradable compound (B) is preferably from 100 to 500000, more preferably from 100 to 200000.

The compound represented by the following formula (18), its hydrolyzate or condensate, is also used as an indecomposable compound (B):

R $\genfrac{}{}{0ex}{}{\text{213}}{\text{n}}$ Si (OR ²¹⁴ ) _4-n (18)

where R ²¹³ and R ²¹⁴ may be the same or different and each represents a monovalent organic group, and n is an integer from 0 to 2.

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. Examples of the alkyl group include methyl, ethyl, propyl and butyl, among which an alkyl group containing from 1 to 5 carbon atoms is preferred. The alkyl group may be linear or branched and may contain a halogen atom such as a fluorine atom replacing a hydrogen atom. Examples of the aryl group in the above formula (18) include phenyl and naphthyl. In the above formula (18), n is preferably 1 or 2.

Illustrative examples of alkylalkoxysilane represented by the above formula (18) include:

methyltrimethoxysilane, methyltriethoxysilane,

methyltri-n-propoxysilane, methyltriisopropoxysilane,

methyltri-n-butoxysilane, methyltri-sec-butoxysilane,

methyltri-tert-butoxysilane, methyltriphenoxysilane,

ethyltrimethoxysilane, ethyltriethoxysilane,

ethyltri-n-propoxysilane, ethyltriisopropoxysilane,

ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane,

ethyltri-tert-butoxysilane, ethyltriphenoxysilane,

n-propyltrimethoxysilane, n-propyltriethoxysilane,

n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane,

n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane,

n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane,

isopropyltrimethoxysilane, isopropyltriethoxysilane,

isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane,

isopropyltri-n-butoxysilane, isopropyltri-sec-butoxysilane,

isopropyltri-tert-butoxysilane, isopropyltriphenoxysilane,

n-butyltrimethoxysilane, n-butyltriethoxysilane,

n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane,

n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane,

n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane,

sec-butyltrimethoxysilane, sec-butyltriethoxysilane,

sec-butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec-butoxysilane,

sec-butyltri-tert-butoxysilane, sec-butyl triphenoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane,

tert-butyltri-n-propoxysilane, tert-butyltriisopropoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane,

tert-butyltri-tert-butoxysilane, tert-butyltriphenoxysilane,

cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane,

cyclohexyltri-n-propoxysilane, cyclohexyltriisopropoxysilane,

cyclohexyltri-n-butoxysilane, cyclohexyltri-sec-

butoxysilane, cyclohexyltri-tert-butoxysilane,

cyclohexyltriphenoxysilane, norbornyltrimethoxysilane,

norbornyltriethoxysilane, norbornyltri-n-propoxysilane,

norbornyltriisopropoxysilane, norbornyltri-n-butoxysilane,

norbornyltri-sec-butoxysilane, norbornyltri-tert-tert-

butoxysilane, norbornyltriphenoxysilane,

phenyltrimethoxysilane, phenyltriethoxysilane,

phenyltri-n-propoxysilane, phenyltriisopropoxysilane,

phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane,

phenyltri-tert-butoxysilane, phenyltriphenoxysilane,

dimethyldimethoxysilane, dimethyldiethoxysilane,

dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane,

dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane,

dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane,

diethyldimethoxysilane, diethyldiethoxysilane,

diethyldi-n-propoxysilane, diethyldiisopropoxysilane,

diethyldi-n-butoxysilane, diethyl di-sec-butoxysilane,

diethyldi-tert-butoxysilane, diethyl diphenoxysilane,

di-n-propyldimethoxysilane, di-n-propyldiethoxytoxysilane,

di-n-propyldi-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propyldi-n-butoxysilane, di-n-propyldi-sec-butoxysilane,

di-n-propyldi-tert-butoxysilane, di-n-propyldiphenoxysilane,

diisopropyl dimethoxysilane, diisopropyl diethoxysilane,

diisopropyl di-n-propoxysilane, diisopropyl diisopropoxysilane, diisopropyl di-n-butoxysilane, diisopropyl di-sec-butoxysilane,

diisopropyl di-tert-butoxysilane, diisopropyl diphenoxysilane,

di-n-butyldimethoxysilane, di-n-butyldiethoxysilane,

di-n-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane,

di-n-butyldi-n-butoxysilane, di-n-butyldi-sec-butoxysilane,

di-n-butyldi-tert-butoxysilane, di-n-butyldiphenoxysilane,

di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane,

di-sec-butyldi-n-propoxysilane,

di-sec-butyldiisopropoxysilane,

di-sec-butyldi-n-butoxysilane, di-sec-butyldi-sec-

butoxysilane, di-sec-butyldi-tert-butoxysilane, di-sec-butyl diphenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di-tert-butyl diisopropoxyl-di butyldi-n-butoxysilane,

di-tert-butyldi-sec-butoxysilane,

di-tert-butyldi-tert-butoxysilane,

di-tert-butyldiphenoxysilane,

di-tert-butyldimethoxysilane, dicyclohexyl diethoxysilane,

di-tert-butyldi-n-propoxysilane, dicyclohexyl diisopropoxysilane, dicyclohexyl di-n-butoxysilane,

dicyclohexyl di-sec-butoxysilane,

dicyclohexyl di-tert-butoxysilane, dicyclohexyl diphenoxysilane, di-tert-butyldimethoxysilane,

dinorbornyl diethoxysilane, di-tert-butyldi-n-propoxysilane,

dinorbornyl diisopropoxysilane, dinorbornyl di-n-butoxysilane, dinorbornyl di-sec-butoxysilane,

dinorbornyl di-tert-butoxysilane, dinorbornyl diphenoxysilane,

diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldiisopropoxysilane, diphenyl di-n-butoxysilane, diphenyl-di-sec-butoxysilane, diphenyldi-tert-butoxysilane, diphenyldiphenoxysilane,

γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,

γ-glycidyloxypropyltrimethoxysilane,

γ-glycidyloxypropyltriethoxysilane,

γ-trifluoropropyltrimethoxysilane and

γ-trifluoropropyltriethoxysilane. You can also use compounds where fluorine atoms replace some or all of the hydrogen atoms. Such alkyl alkoxysilanes can be used alone or as a combination of two or more.

Among the compounds represented by the above formula (18), alkyltrialkoxysilanes of the formula (18) in which n is 1 are particularly preferred. Among them, methyltrimethoxysilane and methyltriethoxysilane are preferred. When methyltrimethoxysilane and / or methyltriethoxysilane is used (used) in an amount of 70 mol% or more based on the total amount of alkyl alkoxysilanes, a cured product is obtained having a good ratio between heat resistance and refractive index. The hydrolyzate and condensate of the compound represented by the above formula (18) are more preferred than the compound represented by the above formula (18). When component (B) is a condensate of the compound represented by the above formula (18), it preferably has a weight average molecular weight of 500 to 100,000 in polystyrene units.

When the hydrolyzate and / or condensate of the compound represented by the above formula (18) is used as component (B), the hydrolytic and / or condensation reaction is carried out in the presence of water and a suitable catalyst, as will be described below.

Specifying more specifically, the compound represented by the above formula (18) is dissolved in a suitable organic solvent, and water is periodically or continuously added to this solution. The catalyst may be previously dissolved or dispersed in an organic solvent, or dissolved or dispersed in added water.

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

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

The amount of water is preferably from 0.25 to 3 mol, particularly preferably from 0.3 to 2.5 mol based on 1 mol of all groups represented by R ²¹⁴ O- in the compound represented by the above formula (18).

The catalyst for hydrolysis and / or condensation of the compound represented by the above formula (18) is an internal complex (chelate) metal compound, organic acid, inorganic acid, organic base or inorganic base.

Illustrative examples of a metal chelate compound used as a catalyst include titanium chelate compounds, such as:

triethoxy mono (acetylacetonato) titanium,

tri-n-propoxy mono (acetylacetonato) titanium,

tri-iso-propoxy mono (acetylacetonato) titanium,

tri-n-butoxy mono (acetylacetonato) titanium,

tri-sec-butoxy mono (acetylacetonato) titanium,

tri-tert-butoxy mono (acetylacetonato) titanium,

diethoxy bis (acetylacetonato) titanium,

di-n-propoxy bis (acetylacetonato) titanium,

di-iso-propoxy bis (acetylacetonato) titanium,

di-n-butoxy bis (acetylacetonato) titanium,

di-sec-butoxy bis (acetylacetonato) titanium,

di-tert-butoxy bis (acetylacetonato) titanium,

monoethoxy tris (acetylacetonato) titanium,

mono-n-propoxy tris (acetylacetonato) titanium,

mono-iso-propoxy tris (acetylacetonato) titanium,

mono-n-butoxy tris (acetylacetonato) titanium,

mono-sec-butoxy tris (acetylacetonato) titanium,

mono-tert-butoxy tris (acetylacetonato) titanium,

tetrakis (acetylacetonato) titanium,

triethoxy mono (ethyl acetoacetate) titanium,

tri-n-propoxy mono (ethyl acetoacetate) titanium,

tri-iso-propoxy mono (ethyl acetoacetate) titanium,

tri-n-butoxy mono (ethyl acetoacetate) titanium,

tri-sec-butoxy mono (ethyl acetoacetate) titanium,

tri-tert-butoxy mono (ethyl acetoacetate) titanium,

diethoxy bis (ethyl acetoacetate) titanium,

di-n-propoxy bis (ethyl acetoacetate) titanium,

di-iso-propoxy bis (ethyl acetoacetate) titanium,

di-n-butoxy bis (ethyl acetoacetate) titanium,

di-sec-butoxy bis (ethyl acetoacetate) titanium,

di-tert-butoxy bis (ethyl acetoacetate) titanium,

monoethoxy tris (ethyl acetoacetate) titanium,

mono-n-propoxy tris (ethyl acetoacetate) titanium,

mono-iso-propoxy tris (ethyl acetoacetate) titanium,

mono-n-butoxy tris (ethyl acetoacetate) titanium,

mono-sec-butoxy tris (ethyl acetoacetate) titanium,

mono-tert-butoxy tris (ethyl acetoacetate) titanium,

tetrakis (ethyl acetoacetate) titanium,

mono (acetylacetonato) tris (ethyl acetoacetate) titanium,

bis (acetylacetonato) bis (ethyl acetoacetate) titanium and

Tris (acetylacetonato) mono (ethyl acetoacetate) titanium;

zirconium chelates, such as:

triethoxy mono (acetylacetonato) zirconium,

tri-n-propoxy mono (acetylacetonato) zirconium,

tri-iso-propoxy mono (acetylacetonato) zirconium,

tri-n-butoxy mono (acetylacetonato) zirconium,

tri-sec-butoxy mono (acetylacetonato) zirconium,

tri-iso-butoxy mono (acetylacetonato) zirconium,

diethoxy bis (acetylacetonato) zirconium,

di-n-propoxybis (acetylacetonato) zirconium,

di-iso-propoxy bis (acetylacetonato) zirconium,

di-n-butoxy bis (acetylacetonato) zirconium,

di-sec-butoxy bis (acetylacetonato) zirconium,

di-tert-butoxy bis (acetylacetonato) zirconium,

monoethoxy tris (acetylacetonato) zirconium,

mono-n-propoxy tris (acetylacetonato) zirconium,

mono-iso-propoxy tris (acetylacetonato) zirconium,

mono-n-butoxy tris (acetylacetonato) zirconium,

mono-sec-butoxy tris (acetylacetonato) zirconium,

mono-iso-butoxy tris (acetylacetonato) zirconium,

tetrakis (acetylacetonato) zirconium,

triethoxy mono (ethyl acetoacetate) zirconium,

tri-n-propoxy mono (ethyl acetoacetate) zirconium,

tri-iso-propoxy mono (ethyl acetoacetate) zirconium,

tri-n-butoxy mono (ethyl acetoacetate) zirconium,

tri-sec-butoxy mono (ethyl acetoacetate) zirconium,

tri-tert-butoxy mono (ethyl acetoacetate) zirconium,

diethoxy bis (ethyl acetoacetate) zirconium,

di-n-propoxy bis (ethyl acetoacetate) zirconium,

di-iso-propoxy bis (ethyl acetoacetate) zirconium,

di-n-butoxy bis (ethyl acetoacetate) zirconium,

di-sec-butoxy bis (ethyl acetoacetate) zirconium,

di-tert-butoxy bis (ethyl acetoacetate) zirconium,

monoethoxy tris (ethyl acetoacetate) zirconium,

mono-n-propoxy tris (ethyl acetoacetate) zirconium,

mono-iso-propoxy tris (ethyl acetoacetate) zirconium,

mono-n-butoxy tris (ethyl acetoacetate) zirconium,

mono-sec-butoxy tris (ethyl acetoacetate) zirconium,

mono-iso-butoxy tris (ethyl acetoacetate) zirconium,

tetrakis (ethyl acetoacetate) zirconium,

mono (acetylacetonato) tris (ethyl acetoacetate) zirconium,

bis (acetylacetonato) bis (ethyl acetoacetate) zirconium and

tris (acetylacetonato) mono (ethyl acetoacetate) zirconium;

and chelated aluminum compounds, such as:

tris (acetylacetonato) aluminum and

Tris (ethyl acetoacetate) aluminum.

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, methyl malonic acid, adipic acid sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid lot, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloracetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid. malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid and tartaric acid.

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

Examples of the organic base used as the catalyst include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine,

monomethyldiethanolamine, triethanolamine, diazabicyclooctane,

diazabicyclononan, diazabicycloundecene and

hydroxide tetramethylammonium.

Examples of the inorganic base used as the catalyst include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide and calcium hydroxide.

Of these, a metal chelate (organic acid) compound, organic acid and an inorganic acid are preferably used as catalyst, and more preferably a titanium chelate compound and an organic acid are used.

As a catalyst, these compounds can be used individually or as a combination of two or more of them.

The amount of catalyst is usually from 0.001 to 10 parts by weight, preferably from 0.01 to 10 parts by weight based on 100 parts by weight of the compound represented by the above formula (18) in units of SiO ₂ .

In addition, it is preferable to remove residual water and alcohol formed as a by-product after hydrolysis and / or condensation of the compound represented by the above formula (18).

The amount of component (B) is preferably from 10 to 95 parts by weight, more preferably from 10 to 90 parts by weight, even more preferably from 20 to 90 parts by weight, particularly preferably from 20 to 70 parts by weight based on 100 parts by weight of the total number of components (A) and (B). When the amount of component (B) is less than 10 parts by weight, the resulting material with a variable refractive index tends to be brittle, and when the amount exceeds 90 parts by weight, the difference in the obtained refractive indices tends to be insignificant.

Sensitive decomposing substance (C)

The radiation-sensitive decomposing substance (C) used in the present invention may be a radiation-sensitive acid generator or a radiation-sensitive base generator. In this case, it is preferable to use an irradiation-sensitive acid generating agent as an irradiation-sensitive decomposing substance (C) when an acid-degradable polymer is used as the degradable polymer (A); and, conversely, a radiation-sensitive base generator as a radiation-sensitive decomposing substance (C) when a base-decomposable polymer is used as a degradable polymer (A).

The above radiation-sensitive acid generator may be trichloromethyl-s-triazine, a diaryliodonium salt, a triarylsulfonium salt, a quaternary ammonium salt or a sulfonic acid ester.

Examples of trichloromethyl-s-triazine 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 and 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6 bis (trichloromethyl) -s-triazine.

Examples of the above diaryliodonium salt include: diphenyl iodonium tetrafluoroborate, hexafluorophosphonate

diphenyliodonium, diphenyliodonium hexafluoroarsenate,

diphenyl iodonium trifluoromethanesulfonate, trifluoroacetate

diphenyliodonium, diphenyliodonium p-toluenesulfonate,

butyltris (2,6-difluorophenyl) diphenyliodonium borate,

hexyltris (p-chlorophenyl) diphenyliodonium borate,

hexyltris (3-trifluoromethylphenyl) diphenyliodonium borate,

4-methoxyphenyl phenyl iodonium tetrafluoroborate,

4-methoxyphenylphenyliodonium hexafluorophosphonate,

4-methoxyphenylphenyliodonium hexafluoroarsenate,

4-methoxyphenylphenyliodonium trifluoromethanesulfonate,

4-methoxyphenyl phenyl iodonium trifluoroacetate,

4-methoxyphenyl phenyl iodonium p-toluenesulfonate,

butyltris (2,6-difluorophenyl) 4-methoxyphenylphenyliodonium borate,

hexyltris (p-chlorophenyl) 4-methoxyphenyl phenyl iodonium borate,

hexyltris (3-trifluoromethylphenyl) 4-methoxyphenylphenyliodonium borate,

bis (4-tert-butylphenyl) iodonium tetrafluoroborate,

bis (4-tert-butylphenyl) iodonium hexafluoroarsenate,

bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate,

bis (4-tert-butylphenyl) iodonium trifluoroacetate,

bis (4-tert-butylphenyl) iodonium p-toluenesulfonate,

butyltris (2,6-difluorophenyl) borate bis (4-tert-butylphenyl) iodonium,

hexyltris (p-chlorophenyl) borate bis (4-tert-butylphenyl) iodonium and hexyltris (3-trifluoromethylphenyl) borate bis (4-tert-butylphenyl)

iodonium.

Examples of the above triaryl sulfonium salt include: triphenyl sulfonium tetrafluoroborate, triphenyl sulfonium hexafluorophosphonate, triphenyl sulfonium hexafluoro arsenate,

triphenylsulfonium trifluoromethanesulfonate, trifluoroacetate

triphenylsulfonium, triphenylsulfonium p-toluenesulfonate,

butyltris (2,6-difluorophenyl) triphenylsulfonium borate,

hexyltris (p-chlorophenyl) triphenylsulfonium borate,

hexyltris (3-trifluoromethylphenyl) triphenylsulfonium borate,

4-methoxyphenyl diphenyl sulfonium tetrafluoroborate,

4-methoxyphenyl diphenylsulfonium hexafluorophosphonate,

4-methoxyphenyl diphenylsulfonium hexafluoroarsenate,

4-methoxyphenyl diphenylsulfonium trifluoromethanesulfonate,

4-methoxyphenyl diphenylsulfonium trifluoroacetate,

4-methoxyphenyl diphenyl sulfonium p-toluenesulfonate,

butyltris (2,6-difluorophenyl) 4-methoxyphenyl diphenylsulfonium borate,

4-methoxyphenyl diphenyl sulfonium hexyltris (p-chlorophenyl) borate, hexyltris (3-trifluoromethylphenyl) borate

4-methoxyphenyl diphenylsulfonium,

4-phenylthiophenyl diphenylsulfonium tetrafluoroborate,

4-phenylthiophenyl diphenylsulfonium hexafluorophosphonate,

4-phenylthiophenyl diphenylsulfonium hexafluoroarsenate,

4-phenylthiophenyl diphenylsulfonium trifluoromethanesulfonate,

4-phenylthiophenyl diphenylsulfonium trifluoroacetate,

4-phenylthiophenyl diphenyl sulfonium p-toluenesulfonate,

4-phenylthiophenyl diphenylsulfonium butyltris (2,6-difluorophenyl) borate,

4-phenylthiophenyl diphenyl sulfonium hexyltris (p-chlorophenyl) borate, hexyltris (3-trifluoromethylphenyl) borate

4-phenylthiophenyl diphenylsulfonium,

(4-hydroxy-1-naphthalenyl) dimethyl sulfonium tetrafluoroborate,

(4-hydroxy-1-naphthalenyl) dimethylsulfonium hexafluorophosphonate,

(4-hydroxy-1-naphthalenyl) dimethyl sulfonium hexafluoroarsenate,

4-hydroxy-1-naphthalenyl) dimethylsulfonium trifluoromethanesulfonate,

(4-hydroxy-1-naphthalenyl) dimethylsulfonium trifluoroacetate,

(4-hydroxy-1-naphthalenyl) dimethylsulfonium p-toluenesulfonate, butyltris (2,6-difluorophenyl) borate, (4-hydroxy-1-naphthalenyl)

dimethyl sulfonium, hexyltris (p-chlorophenyl) borate (4-hydroxy-

1-naphthalenyl) dimethylsulfonium and

hexyltris (3-trifluoromethylphenyl) borate (4-hydroxy-1-naphthalenyl)

dimethyl sulfonium.

Examples of the above quaternary ammonium salt include: tetramethyl ammonium tetrafluoroborate, tetramethyl ammonium hexafluorophosphonate, tetramethyl ammonium hexafluoro arsenate, tetramethyl ammonium trifluoromethanesulfonate, tetramethyl ammonium trifluoroacetate, tetramethyl ammonium tetrafluoronetammonium tetrafluoron tetra methyl tetrafluoron tetra methyl tetra methyl tetrafluoronammonium tetrafluoronamide

hexyltris (p-chlorophenyl) tetramethylammonium borate,

hexyltris (3-trifluoromethylphenyl) tetramethylammonium borate

tetrafluoroborate tetrabutylammonium, hexafluorophosphonate

tetrabutylammonium, tetrabutylammonium hexafluoroarsenate,

tetrabutylammonium trifluoromethanesulfonate, trifluoroacetate

tetrabutylammonium, tetrabutylammonium p-toluenesulfonate,

butyltris (2,6-difluorophenyl) tetrabutylammonium borate,

hexyltris (p-chlorophenyl) tetrabutylammonium borate,

hexyltris (3-trifluoromethylphenyl) tetrabutylammonium borate,

benzyltrimethylammonium tetrafluoroborate, hexafluorophosphonate

benzyltrimethylammonium, benzyltrimethylammonium hexafluoroarsenate,

benzyltrimethylammonium trifluoromethanesulfonate, benzyltrimethylammonium trifluoroacetate, benzyltrimethylammonium p-toluenesulfonate,

butyltris (2,6-difluorophenyl) benzyltrimethylammonium borate,

hexyltris (p-chlorophenyl) benzyltrimethylammonium borate,

hexyltris (3-trifluoromethylphenyl) benzyltrimethylammonium borate,

benzyldimethylphenylammonium tetrafluoroborate, benzyldimethylphenylammonium hexafluorophosphonate, hexafluoroarsenate

benzyldimethylphenylammonium trifluoromethanesulfonate

benzyldimethylphenylammonium trifluoroacetate

benzyldimethylphenylammonium, p-toluenesulfonate

benzyldimethylphenylammonium, butyltris (2,6-difluorophenyl) borate

benzyldimethylphenylammonium, hexyltris (p-chlorophenyl) borate

benzyldimethylphenylammonium, hexyltris (3-trifluoromethylphenyl)

benzyldimethylphenylammonium borate, tetrafluoroborate

N-cinnamylideneethylphenylammonium hexafluorophosphonate

N-cinnamylideneethylphenylammonium, hexafluoroarsenate

N-cinnamylideneethylphenylammonium trifluoromethanesulfonate

N-cinnamylideneethylphenylammonium trifluoroacetate

N-cinnamylideneethylphenylammonium, p-toluenesulfonate

N-cinnamylideneethylphenylammonium, butyltris (2,6-difluorophenyl)

N-cinnamilideneethylphenylammonium borate, hexyltris (p-chlorophenyl)

N-cinnamilideneethylphenylammonium borate and hexyltris (3-trifluoromethylphenyl) N-cinnamylideneethylphenylammonium borate.

Examples of the above sulfonic acid ester include α-hydroxymethylbenzoin-p-toluenesulfonic ester

acids, ester α-hydroxymethylbenzoin-

trifluoromethanesulfonic acid ester

α-hydroxymethylbenzoin methanesulfonic acid, pyrogallol tri ester (p-toluenesulfonic acid), pyrogallol tri ester (trifluoromethanesulfonic acid), pyrogallol trimethanesulfonic acid ester, ester

2,4-dinitrobenzyl-p-toluenesulfonic acid, 2,4-dinitrobenzyl-trifluoromethanesulfonic acid ester, 2,4-dinitrobenzyl-methanesulfonic acid ester, 2,4-dinitrobenzyl-1,2-naphthoquinondiazido-5-sulfonic ester acids, 2,6-dinitrobenzyl-p-toluenesulfonic acid ester, 2,6-dinitrobenzyl-trifluoromethanesulfonic acid ester, 2,6-dinitrobenzyl-methanesulfonic acid ester, 2,6-dinitrobenzyl-1,2-naphthoquinone diazido ester -5-sulfonic acid, 2-nitrobenzyl-p-toluenesulfonic acid ester lots ester, 2-nitrobenzyl-trifluoromethanesulfonic acid ester, 2-nitrobenzyl-methanesulfonic acid ester, 2-nitrobenzyl-1,2-naftohinondiazido-5-sulfonic acid ester,

4-nitrobenzyl-p-toluenesulfonic acid, ester

4-nitrobenzyl-trifluoromethanesulfonic acid, ester of 4-nitrobenzyl-methanesulfonic acid, ester

4-nitrobenzyl-1,2-naphthoquinondiazido-5-sulfonic acid, N-hydroxynaphthalimide-p-toluenesulfonic acid ester,

N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester, N-hydroxynaphthalimide-methanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboxyimide-p-toluenesulfonic acid ester, N-hydroxy-5-norbornene-2 ester 3-Dicarboxyimide-trifluoromethanesulfonic acid, N-hydroxy-5-norbornene-2,3-dicarboxyimide-methanesulfonic acid ester, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2- naphthoquinondiazido-4-sulfonic acid and 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinondiazido-4-sulfonic ester th acid.

Among these compounds, 2- (3-chlorophenyl) bis (4,6-trichloromethyl) -s-triazine,

2- (4-methoxyphenyl) bis (4,6-trichloromethyl) -s-triazine,

2- (4-methylthiophenyl) bis (4,6-trichloromethyl) -s-triazine,

2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine,

2-piperonyl bis (4,6-trichloromethyl) -s-triazine,

2- [2- (furan-2-yl) ethenyl] bis (4,6-trichloromethyl) -s-triazine,

2- [2- (5-methylfuran-2-yl) ethenyl] bis (4,6-trichloromethyl) -s-triazine,

2- [2- (4-diethylamino-2-methylphenyl) ethenyl] bis (4,6-trichloromethyl) -

s-triazine and 2- (4-methoxynaphthyl) bis (4,6-trichloromethyl) -s-triazine are preferred as trichloromethyl-s-triazines; diphenyliodonium trifluoroacetate,

diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenyl phenyl iodonium trifluoromethanesulfonate and trifluoroacetate

4-methoxyphenylphenyliodonium are preferred as diaryliodonium salts; triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate,

4-methoxyphenyl diphenylsulfonium trifluoromethanesulfonate,

4-methoxyphenyl diphenylsulfonium trifluoroacetate,

4-phenylthiophenyl diphenylsulfonium trifluoromethanesulfonate and

4-phenylthiophenyl diphenylsulfonium trifluoroacetate are preferred as triarylsulfonium salts; butyltris (2,6-difluorophenyl) tetramethylammonium borate,

hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, tetramethylammonium butiltris (2,6-difluorophenyl) borate benzildimetilfenilammoniya, hexyltris (p-chlorophenyl) borate and benzildimetilfenilammoniya hexyltris (3-trifluoromethylphenyl) borate are preferred benzildimetilfenilammoniya as quaternary ammonium salts; and 2,6-dinitrobenzyl-p-toluenesulfonic acid ester, 2,6-dinitrobenzyl-trifluoromethanesulfonic ester

acids, N-hydroxynaphthalimide-p-toluenesulfonic ester

acids and N-hydroxynaphthalimide ester-

trifluoromethanesulfonic acid are preferred as sulfonic acid esters.

What is described in Japanese Patent JP-A4-330444, Polymer Publication, pp. 242-248, vol. 46, No.6 (1997) and US Pat. No. 5,627,010 are preferably used as the above radiation sensitive base generator. However, a radiation sensitive base generator is not limited to these compounds if it generates a base when exposed to radiation.

The radiation sensitive base generator in the present invention is preferably an optically active carbamate such as triphenylmethanol, benzyl carbamate or benzoincarbamate; amide such as

O-carbamoyl hydroxylamide, O-carbamoyloxime, aromatic sulfonamide, alpha-lactam or N- (2-allylethynyl) amide or other amides; ester oxime, α-aminoacetophenone or cobalt complex.

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

where R ⁷⁶ represents an alkyl group containing from 1 to 6 carbon atoms, an alkoxyl group containing from 1 to 6 carbon atoms, a thioalkyl group containing from 1 to 6 carbon atoms, a dialkylamino group containing from 1 to 6 carbon atoms, piperidyl group, nitro group, hydroxy group, mercapto group, aryl group, fluorine atom, chlorine atom or bromine atom, k represents an integer from 0 to 3, R ⁷⁷ represents a hydrogen atom, an alkyl group containing from 1 to 6 carbon atoms or an aryl group, and R ⁷⁸ and R ⁷⁹ each independently, represent a hydrogen atom, an alkyl group containing from 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ⁷⁸ and R ⁷⁹ may be linked together to form a cyclic structure containing 5-6 carbon atoms, together with a nitrogen atom with which they are associated

where R ⁸⁰ represents an alkyl group containing from 1 to 6 carbon atoms, an alkoxyl group containing from 1 to 6 carbon atoms, a thioalkyl group containing from 1 to 6 carbon atoms, a dialkylamino group containing from 1 to 6 carbon atoms, piperidyl a group, a nitro group, a hydroxy group, a mercapto group or an aryl group, R ⁸¹ represents a hydrogen atom, an alkyl group containing from 1 to 6 carbon atoms, or an aryl group, and R ⁸² and R ⁸³ each independently represent a hydrogen atom an alkyl group containing from 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ⁸² and R ⁸³ may be bonded together to form a cyclic structure containing 5-6 carbon atoms, together with the nitrogen atom to which they are attached,

where R ⁸⁴ represents an alkyl group containing from 1 to 6 carbon atoms, or an aryl group, and R ⁸⁵ and R ⁸⁶ each independently represent a hydrogen atom, an alkyl group containing from 1 to 6 carbon atoms, an aryl group or benzyl a group, or R ⁸⁵ and R ⁸⁶ may be bonded together to form a cyclic structure containing 5-6 carbon atoms, together with the nitrogen atom to which they are bonded,

where R ⁸⁷ and R ⁸⁸ each independently represent an alkyl group containing from 1 to 6 carbon atoms, or an aryl group,

where R ⁸⁹ , R ⁹⁰ and R ⁹¹ each independently represent an alkyl group containing from 1 to 6 carbon atoms, or an aryl group,

where R ⁹² represents an alkyl group containing from 1 to 6 carbon atoms, an alkoxyl group containing from 1 to 6 carbon atoms, a thioalkyl group containing from 1 to 6 carbon atoms, a dialkylamino group containing from 1 to 6 carbon atoms, piperidyl a group, a nitro group, a hydroxy group, a mercapto group or an aryl group, R ⁹³ represents a hydrogen atom, an alkyl group containing from 1 to 6 carbon atoms, or an aryl group, and R ⁹⁴ , R ⁹⁵ and R ⁹⁶ each independently represent a hydrogen atom, an alkyl group containing from 1 to 6 carbon atoms, an aryl group or a benzyl group,

where R ⁹⁷ represents an alkyl group containing from 1 to 6 carbon atoms, an alkoxyl group containing from 1 to 6 carbon atoms, a thioalkyl group containing from 1 to 6 carbon atoms, a dialkylamino group containing from 1 to 6 carbon atoms, piperidyl a group, a nitro group, a hydroxy group, a mercapto group or an aryl group, 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 containing from 1 to 6 carbon atoms fluorine atom, chlorine atom pa, a bromine atom or an aryl group, and R ¹⁰⁰ and R ¹⁰¹ each independently represent a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ¹⁰⁰ and R ¹⁰¹ may be bonded together with the formation of a cyclic structure containing 5-6 carbon atoms, together with the nitrogen atom to which they are attached,

where R ¹⁰² and R ¹⁰³ each independently represent an alkyl group containing from 1 to 6 carbon atoms, an alkoxyl group containing from 1 to 6 carbon atoms, a thioalkyl group containing from 1 to 6 carbon atoms, a dialkylamino group containing from 1 to 6 carbon atoms, a piperidyl group, a nitro group, a hydroxy group, a mercapto group or an aryl group, R ¹⁰⁴ -R ¹⁰⁷ each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, a cyano group, a phenoxy group, an alkyl group, containing from 1 to 6 carbon atoms a carbon atom, a fluorine atom, a chlorine atom, a bromine atom or an aryl group, and A ⁵ is a divalent group of atoms formed by the exclusion of two hydrogen atoms bonded to one or two nitrogen atoms of monoalkylamine, piperazine, aromatic diamine or aliphatic diamine,

where R ¹⁰⁸ and R ¹⁰⁹ each independently represent an alkyl group containing from 1 to 6 carbon atoms, an alkoxyl group containing from 1 to 6 carbon atoms, a thioalkyl group containing from 1 to 6 carbon atoms, a dialkylamino group containing from 1 to 6 carbon atoms, a piperidyl group, a nitro group, a hydroxy group, a mercapto group or an aryl group, R ¹¹⁰ and R ¹¹¹ each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, a cyano group, a phenoxy group, an alkyl group, containing from 1 to 6 carbon atoms a carbon atom, a fluorine atom, a chlorine atom, a bromine atom or an aryl group, R ¹¹² -R ¹¹⁵ each independently represents a hydrogen atom, an alkyl group containing from 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ¹¹² and R ¹¹³ , and R ¹¹⁴ and R ¹¹⁵ , can be bonded together to form a cyclic structure containing 5-6 carbon atoms, together with the nitrogen atom to which they are bonded, and A ⁵ represents an alkylene group containing from 1 to 6 carbon atoms a cyclohexylene group, a phenylene group or a single bond,

where R ¹¹⁶ -R ¹¹⁸ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group containing from 1 to 6 carbon atoms, an alkenyl group containing from 1 to 6 carbon atoms, an alkynyl group containing from 1 to 6 carbon atoms, an alkoxyl group containing from 1 to 6 carbon atoms, or an aryl group,

where L represents at least one ligand selected from the group comprising ammonia, pyridine, imidazole, ethylenediamine, trimethylenediamine, tetramethylenediamine,

hexamethylenediamine, propylene diamine, 1,2-cyclohexanediamine, N, N-diethylenediamine and diethylene triamine, m is an integer from 2 to 6, R ¹¹⁹ is an aryl group, and R ¹²⁰ is an alkyl group containing from 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 includes an alkenyl group, such as vinyl or propylene; an alkynyl group such as acetylenyl; a phenyl group, a naphthyl group and anthracenyl group, and those also containing a fluorine atom, a chlorine atom, a bromine atom, a haloalkyl group, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, an azido group, a dialkylamino group, an alkoxy group or a thioalkyl group replacing hydrogen atoms in the above groups.

Among such radiation sensitive base generators, preferred are

2-nitrobenzylcyclohexylcarbamate, triphenylmethanol,

o-carbamoyl hydroxylamide, 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, tris (triphenylmethyl borate) hexaaminocobalt (III) and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone.

The above radiation sensitive decomposing substance (C) is preferably used in an amount of from 0.01 parts or more by weight, more preferably from 0.05 parts or more by weight based on 100 parts by weight of the total amount of degradable polymer (A) and non-degradable compound (B). When the amount of component (C) is less than 0.01 parts by weight, the sensitivity to radiation tends to be lower. The upper limit value is preferably 30 parts by weight, more preferably 20 parts by weight.

Stabilizer (D)

The function of the stabilizer (D) used in the present invention is to stabilize the residual degradable polymer (A) existing in the material with a variable refractive index after exposure to radiation to ensure stability to acid or base. Such stabilization prevents a change in the refractive index and, consequently, a deterioration in the structure with the distribution of the refractive index obtained by the method of the present invention, even when used under conditions where the light passing through it has a wavelength close to the wavelength used to change the refractive index.

Examples of the above stabilizer (D) include an amino compound, an epoxy compound, a thiran compound, an oxetane compound, an alkoxymethylmelamine compound, an alkoxymethylglucoluryl compound, a compound

alkoxymethylbenzoguanamine, alkoxymethylurea compound, isocyanate compound, cyanate compound, oxazoline compound, oxazine compound and silyl compound (silyl halide compound and other silyl compounds).

Examples of the above amino compounds include ammonia, trimethylamine, triethylamine, tripropylamine,

tributylamine, tripentylamine, trihexylamine,

tricyclohexylamine, triphenylamine, tribenzylamine, aniline, ethylenediamine, diethylene triamine, triethylenetetramine,

tetraethylenepetamine, 1,3-diaminopropane, 1,4-diaminobutane,

1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane,

1,8-diamino-octane, 1,9-diaminononan, 1,10-diaminodecane,

1,11-diaminoundecane, 1,12-diaminododecane,

1,4-diaminocyclohexane, 1,3-cyclohexanbis (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, amidol, 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-benzene tetramine, 2,4-diamino-1,3,5-triazine, 4,4'-diaminobenzophenone,

3.3 ’, 4,4'-tetraaminobenzophenone, triaminobenzene,

4,4’-thiodianiline, 2,3,5,6-tetrabrom-p-xylylenediamine,

2,3,5,6-tetrachloro-p-xylylenediamine, 4,5-methylenedioxy-1,2-

phenylenediamine and 2,2'-bis (5-aminopyridyl) sulfide.

The above epoxy compound is an epoxy resin of bisphenol A, an epoxy resin of bisphenol F, a phenolic novolac epoxy resin, a cresol novolac epoxy resin, a cyclic aliphatic epoxy resin, or an aliphatic polyglycidyl ether.

Examples of commercially available products of the above compounds are given below. Commercially available epoxy resins of bisphenol A include Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010 and 828 (from Yuka Shell Epoxy Co., Ltd.), epoxy resins of bisphenol F include Epicoat 807 (from Yuka Shell Epoxy Co., Ltd.), phenolic novolac epoxy resin products include Epicoat 152 and 154 (from Yuka Shell Epoxy Co., Ltd.) and EPPN201 and 202 (from Nippon Kayaku Co., Ltd.), cresol novolac epoxy resin products include EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (from Nippon Kayaku Co., Ltd.) and Epicoat 180S75 (from Yuka Shell Epoxy Co., Ltd.), cyclic aliphatic epoxy resin products include CY175, CY177 and CY179 (from CIBA-GEIGY AG), E RL-4234, ERL-4299, ERL-4221 and ERL-4206 (From UCC Co., Ltd.), Showdyne 509 (from Showa Denko KK), Araldyte CY-182, CY-192 and CY-184 (from CIBA- GEIGY AG), Epichlon 200 and 400 (from Dainippon Ink and Chemicals, Inc.), Epicoat 871 and 872 (from Yuka Shell Epoxy Co., Ltd.) and ED-5661 and ED-5662 (from Ceranies Coating Co., Ltd ), and aliphatic polyglycidyl ether products include Epolite 100MF (from Kyoeisha Kagaku Co., Ltd.) and Epiol TMP (from NOF Corporation).

In addition to the above compounds, phenyl glycidyl ether, butyl glycidyl ether,

3,3,3-trifluoromethylpropylene oxide, styrene oxide,

haksafluoropropylene oxide, cyclohexene oxide,

N-glycidylphthalimide, (nonafluoro-N-butyl) epoxide,

perfluoroethyl glycidyl ether, epichlorohydrin,

epibromohydrin, N, N-diglycidylaniline and

3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane.

Examples of the above thiran compound include those obtained by replacing epoxy groups in the above epoxy compounds with an ethylene sulfide group, as shown, for example, in J. Org. Chem., 28, 229 (1963).

Examples of the above oxetane compound include bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (trade name XDO from Toagosei Chemical Industry 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) methylphenyl] sulfone,

bis [(3-ethyl-3-oxetanylmethoxy) methylphenyl] ketone,

bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] hexafluoropropane, tri [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and

tetra [(3-ethyl-3-oxetanylmethoxy) methyl] benzene.

The above alkoxymethylmelamine compound,

the alkoxymethylbenzoguanamine compound, the alkoxymethylglucoluryl compound and the alkoxymethylurea compound are obtained by replacing the methylol groups with a methylolmelamine compound, a methylolbenzoguanamine compound, a methyloglucoluryl compound and a methylolurea compound with an alkoxymethyl group, respectively. The type of alkoxymethyl group is not particularly limited, as illustrated by the methoxymethyl group, ethoxymethyl group, propoxymethyl group and butoxymethyl group.

Commercially available products of the above compounds include Simel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 114`, 272, 202, 1156, 1158, 1123, 1170 and 1174 and UFR65 and 300 ( from Mitsui Sianamid Co., Ltd.) and Nicalack Mx-750, Mx-032, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11 and Mw-30 (from Sanwa Chemical Co., Ltd .).

Examples of the above isocyanate compound include phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate,

1-methoxyphenylene-2,4-diisocyanate, 1-methylphenylene-2,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, bisphenylene-4,4 ' -diisocyanate, 3,3'-dimethylbiphenylene-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxyphenylmethane-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 (methyl isocyanate), cyclohexane-1,4-bis (methyl isocyanate)

isophorondiisocyanate, dicyclohexylmethane-2,4’-diisocyanate,

dicyclohexylmethane-4,4’-diisocyanate, ethylenediisocyanate,

tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, dodecamethylene-1,12-diisocyanate, methyl ester of lysinediisocyanate and prepolymers having isocyanate at both ends, obtained by the interaction between a stoichiometrically excess amount of an organic diisocyanate and a bifunctional compound active hydrogen.

The above diisocyanate can be used in combination with an organic polyisocyanate having 3 or more functional groups, such as phenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, diphenylmethane-2,5,4'-triisocyanate , 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 (methyl isocyanate), 3,5-dimethylcyclohexane-1,3,5-

tris (methyl isocyanate), 1,3,5-trimethylcyclohexane-1,3,5-

tris (methyl isocyanate), dicyclohexylmethane-2,4,2’-triisocyanate,

triisocyanate, dicyclohexylmethane-2,4,4'-triisocyanate, or having an isocyanate-terminated prepolymer obtained by reacting between a stoichiometrically excessive amount of an organic polyisocyanate having 3 or more functional groups and a polyfunctional active hydrogen-containing compound having 2 or more functional groups.

Examples of the above cyanate compound include 1,3-dicyanatobenzene, 1,4-dicyanatobenzene,

1,3,5-tricyanatobenzene, 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 benzene polynuclear polyisocyanate compounds obtained by the interaction between a phenolic resin and a cyanogen halide (for example, JP-B 45-11712 and JP-B 55-9433) (the term “JP-B” as used in this description means “publication of an examination of a patent application Japan ”). A divalent cyanate compound derived from bisphenol, such as 2,2-bis (4-cyanatophenyl) propane, is particularly preferred since it is readily available (available), has excellent formability, and confers favorable properties to the final vulcanized product. You can also use the polycyanate obtained by the interaction of the initial condensate of phenol and formaldehyde with a cyano halide.

Examples of the above oxazoline compound include 2,2'-bis (2-oxazolin), 4-furan-2-ylmethylene-2-phenyl-4H-oxazol-5-one, 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-oxazolin,

2,6-bis (isopropyl-2-oxazolin-2-yl) pyridine,

2,2’-isopropylidenebis (4-tert-butyl-2-oxazoline),

2,2'-isopropylidenebis (4-phenyl-2-oxazoline),

2,2’-methylenebis (4-tert-butyl-2-oxazoline) and

2,2’-methylenebis (4-phenyl-2-oxazoline).

Examples of the above 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'-isopropylidenebis (4-tert-butyl-2-oxazine),

2,2'-isopropylidenebis (4-phenyl-2-oxazine), 2,2'-methylenebis (4-tert-butyl-2-oxazine) and 2,2'-methylenebis (4-phenyl-2-oxazine).

Examples of the above silyl halide compound include tetrahalogenosilanes such as tetrachlorosilane, tetrabromosilane, tetraiodosilane, trichlorobromosilane and

dichlorodibromosilane; monoalkyltrihalogenosilanes such as methyltrichlorosilane, methyldichlorobromosilane and

cyclohexyl trichlorosilane; monoaryltrihalogenosilanes such as phenyltrichlorosilane, naphthyltrichlorosilane,

4-chlorophenyl trichlorosilane and phenyl dichlorobromosilane;

monoaryloxytrihalogenosilanes such as phenoxytrichlorosilane and phenoxydichlorobromosilane; monoalkoxytrihalogenosilanes such as methoxytrichlorosilane and ethoxytrichlorosilane;

dialkyl dihalogenosilanes such as dimethyldichlorosilane,

methyl (ethyl) dichlorosilane and methyl (cyclohexyl) dichlorosilane;

monoalkylmonoaryl dihalogenosilanes such as methyl (phenyl)

dichlorosilane; diaryldihalogenosilanes such as

diphenyldichlorosilane; diaryloxyhalogenosilanes such as diphenoxydichlorosilane; monoalkylmonoaryloxyhalogenosilanes,

such as methyl (phenoxy) dichlorosilane;

monoarylmonoaryloxyhalogenosilanes such as phenyl (phenoxy)

dichlorosilane; dialkoxydigelogenosilanes such as

diethoxydichlorosilane; monoalkyl monoalkoxy dichlorosilanes such as methyl (ethoxy) dichlorosilane; monoarylmonoethoxy dichlorosilanes such as phenyl (ethoxy) dichlorosilane; trialkyl monohalogenosilanes,

trialkyl monohalogenosilanes such as trimethylchlorosilane, dimethyl (ethyl) chlorosilane and dimethyl (cyclohexyl) chlorosilane;

dialkylmonoarylmonohalogenosilanes such as dimethyl (phenyl)

chlorosilane; monoalkyl diaryl monohalogenosilanes such as methyl (diphenyl) chlorosilane; triaryloxymonohalogenosilanes such as triphenoxychlorosilane; monoalkyl-diaryloxymonohalogenosilanes,

such as methyl (diphenoxy) chlorosilane;

monoaryldiaryloxymonohalogenosilanes such as

phenyl (diphenoxy) chlorosilane; dialkylmonoaryloxymonohalogenosilanes such as

dimethyl (phenoxy) chlorosilane; diarylmonoaryloxymonohalogenosilanes such as

diphenyl (phenoxy) chlorosilane; monoalkylmonoarylmonoaryloxymonohalogenosilanes such as

methyl (phenyl) (phenoxy) chlorosilane; triethoximonohalogenosilanes,

such as triethoxychlorosilane; and oligomers thereof, such as a dimer, trimer, tetramer and tetrachlorosilane pentamer.

Examples of the above other silyl compounds include hexamethyldisilazane,

tert-butyldimethylchlorosilane, bis (trimethylsilyl) trifluoroacetamide, diethylaminotrimethylsilane, trimethylsilanol, hexamethyldisiloxane,

chloromethyldimethylethoxysilane, acetyl triphenylsilane,

ethoxytriphenylsilane, triphenylsilanol, triethylsilanol,

tripropylsilanol, tributylsilanol, hexaethyl disiloxane,

trimethylmethoxysilane, trimethylethoxysilane,

triethyl methoxysilane, triethyl ethoxysilane,

acetoxyethyl dimethylchlorosilane,

1,3-bis (hydroxybutyl) tetramethyldisiloxane,

1,3-bis (hydroxypropyl) tetramethyldisiloxane,

γ-aminopropyl-methoxysilane, γ-aminopropylethoxysilane,

N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane,

N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane,

N-phenyl-γ-aminopropyltrimethoxysilane,

γ-anilinopropyltrimethoxysilane,

γ-dibutylaminopropyltrimethoxysilane,

γ-ureidopropyltriethoxysilane, hydrochloride

N-β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane,

γ-methacryloxypropyltrimethoxysilane,

γ-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane,

vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropylmethyldiethoxysilane,

γ-glycidoxypropyltriethoxysilane,

γ- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,

γ-glycidoxypropyltrimethoxysilane,

γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, trimethylchlorosilane, hexamethyldisilazane,

N-trimethylsilylimidazole, bis (trimethylsilyl) urea,

trimethylsilylacetamide, bistrimethylsilylacetamide,

trimethylsilyl isocyanate, trimethylmethoxysilane,

trimethylethoxysilane, methyltrimethoxysilane,

methyltriethoxysilane, dimethyldimethoxysilane,

dimethyldiethoxysilane, tert-butyldimethylchlorosilane,

tert-butyl diphenylchlorosilane, triisopropylchlorosilane,

n-propyltrimethoxysilane, isobutyltrimethoxysilane,

n-hexyltrimethoxysilane, n-decyltrimethoxysilane,

n-hexadecyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, dimethylsilyldiisocyanate, methylsilyl triisocyanate,

phenyltrimethoxysilane, diphenyldimethoxysilane and

phenylsilyl triisocyanate.

Among them, the stabilizer (D) used in the present invention is preferably an amino compound, an epoxy compound, a thiran compound, an oxetane compound, an oxazoline compound, an oxazine compound, a silyl compound, an isocyanate compound or a cyanate compound, more preferably an amino compound, an epoxy compound, a thiran compound, a compound oxetane, an oxazoline compound or an oxazine compound. Ethylene diamine, phenyl glycidyl ether, 3-phenoxypropylene sulfide, 3,3,3-trifluoropropylene oxide are particularly preferred,

hexamethyldisilazane, γ-aminopropylmethoxysilane,

γ-glycidoxypropyltrimethoxysilane or methylsilyl triisocyanate.

These stabilizers (D) can be used individually or as a combination of two or more of them. The amount of component (D) may be excessive, so that the residual degradable polymer (A) can interact completely, but usually it is 10 parts or more by weight, preferably 30 parts or more by weight based on 100 parts by weight of component (A) . When the amount of component (D) is less than 10 parts by weight, the stability of a material with a variable refractive index may be unsatisfactory due to incomplete interaction.

A catalyst may be used in combination with a stabilizer (D). The use of a catalyst promotes the reaction (i.e., facilitates its progression) between component (D) and the residual degradable polymer (A).

The catalyst is an acid catalyst, a basic catalyst or a quaternary onium salt.

Examples of the acid catalyst include organic acids such as acetic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid and trifluoromethanesulfonic acid; and inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid. Examples of a basic catalyst include alkali metal carbonates such as sodium carbonate, potassium carbonate and lithium carbonate; alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate and lithium bicarbonate; alkali metal acetates such as sodium acetate; alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide and lithium methoxide; alkali metal mercaptans such as sodium methyl mercaptan and sodium ethyl mercaptan; organic amines such as 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 (DABCO) and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU); alkyl lithium, such as methyl lithium, ethyl lithium and butyl lithium; and lithium alkyl amides such as lithium diisopropylamide and lithium dicyclohexylamide. Examples of the above quaternary onium salts include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium acetate, tetrabutylammonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, cetyltrimethylammonium bromide, tetraethylammonium bromide. Also, a combination of 18-crown-6-ether and salts such as potassium chloride, potassium bromide, potassium iodide, cesium chloride, potassium phenoxide, sodium phenoxide or potassium benzoate can be used as a catalyst.

Among them, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, sodium hydroxide, potassium tert-butoxide, triethylamine, DBU, tetrabutylammonium bromide, tetrabutylphosphonium bromide and a mixture of 18-crown-6-ether / potassium phenoxide are preferred as a catalyst.

The amount of catalyst is preferably 2 mol or less based on 1 equivalent of component (D) if the component (D) is an amino compound, an alkoxymethylmethamine compound, an alkoxymethylglucoluryl compound, an alkoxymethylbenzoguanamine compound, an alkoxymethylbenzoguanamine compound, an alkoxymethylmethylmethyl compound.

When an epoxy compound, a thiran compound, an oxetane compound, an isocyanate compound, a cyanate compound, an oxazoline compound, an oxazine compound or another silyl compound are used as component (D), 0.2 mol or less based on 1 equivalent of component (D) is preferably used.

The number of equivalents of component (D) is obtained by multiplying the number of reactive groups contained in component (D) by the amount (mol) of component (D), and the number of reactive is determined as follows in accordance with the type of component (D).

amino compound: number of nitrogen atoms

epoxy compound: number of epoxy groups

thiran compound: number of ethylene sulfide groups

oxetane compound: number of oxetanyl groups

alkoxymethylmelamine compound, compound

alkoxymethylglucoluryl, alkoxymethylbenzoguanamine compound

and alkoxymethylurea compound: number of alkoxymethyl groups

isocyanate compound: number of isocyanate groups

cyanate compound: number of cyanate groups

oxazoline compound: number of oxazolyl groups

oxazine compound: number of oxazyl groups

silyl halide compound: number of halogen atoms bonded to silicon atoms

other silyl compounds: number of silicon atoms

Other components

The variable refractive index composition used in the present invention may contain other additives within those that do not adversely affect the object of the present invention. Additives include an ultraviolet light absorber, a sensitizer, a surfactant, a heat resistance improver, and an adhesive adjuvant.

The above ultraviolet light absorber is benzotriazole, salicylate, benzophenone, substituted acrylonitrile, xanthan, coumarin, flavone or chalcon. Specific examples of an ultraviolet light absorber include Tinubin 234 (2- (2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl) -2H-benzotriazole), Tinubin 571 (a derivative of hydroxyphenylbenzotriazole) and Tinubin 1130 (methyl condensate -3- (3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl) propionate and polyethylene glycol (molecular weight 300)) (Ciba Specialty Chemicals) and 1,7-bis (4-hydroxy -3-methoxyphenyl) -1,6-heptadiene-3,5-dione and dibenzylideneacetone.

When an ultraviolet light absorber is added, the amount of acid or base formed from component (C) may gradually decrease with increasing depth from the surface of the irradiated portion of the composition with a varying refractive index, which is useful as a means of forming a GRIN type product. The amount of ultraviolet light absorber is preferably 30 parts or less by weight, more preferably 20 parts or less by weight based on 100 parts by weight of the total amount of components (A) and (B).

The above sensitizer is, for example, coumarin having a substituent at the 3-position and / or 7-position, flavone, dibenzalacetone, dibenzylcyclohexane, chalcone, xanthene, thioxanthene, porphyrin, phthalocyanine, acridine or anthracene.

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

The above surfactant can be added to improve the coating ability, for example, to prevent furrowing or to improve the developmental ability.

Examples of a surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, including

polyoxyethylene lauryl ether,

polyoxyethylene stearyl ether and

polyoxyethylene oleyl ether; polyoxyethylene aryl ethers, including polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; and polyethylene glycol dialkyl esters, including polyethylene glycol dilaurate and polyethylene glycol distearate; fluorinated surfactants such as Top EF301, EF303 and EF352 (from Shin Akitakasei Co., Ltd.), available under their trade names, Megafac F171, F172 and F173 (from Dainippon Ink and Chemicals, Inc.), Florade FC430 and FC431 (from Sumitоmo 3M Limited) and Asahi Guard AG710, Surflon S-382, SC-102, SC-103, SC-104, SC-105 and SC-106 (from Asahi Glass Co., Ltd.); other surfactants, such as the organosilicon polymer KP341 (from Shin-Etsu Chemical Co., Ltd.) and (co) polymer based on acrylic or methacrylic acid Polyflow No.57 and No.95 (from Kyoeisha Kagaku Co., Ltd .) which are available under their respective trade names.

The amount of surfactant is preferably 2 parts or less by weight, more preferably 1 part or less by weight based on 100 parts by weight of the total amount of components (A) and (B).

The above adhesive adjuvant may be added to improve adhesion to a substrate (substrate) and is preferably a silane coupling agent.

The above heat resistance improving agent is an unsaturated compound such as polyvalent acrylate.

If necessary, an antistatic agent, a stabilizer of keeping quality (storage), a halo inhibitor, an anti-foaming agent, a pigment and a thermal generator can be additionally added to the material with a variable refractive index used in the present invention.

Formation of a structure with a distribution of refractive index

In the present invention, a structure with a distribution of refractive index can be obtained, for example, from the above composition with a variable refractive index as follows.

First, a composition with a variable refractive index is dissolved or dispersed in a solvent to obtain a composition having a solids content of from 5 to 70 wt.%. If necessary, before use, the composition can be filtered through a filter having a pore diameter of from 0.1 to 10 microns.

After that, this composition is applied to the surface of a substrate, such as a silicon wafer (thin disk), and preliminarily fired to remove the solvent so that a coating film of the composition with a variable refractive index is formed. Parts of the formed coating film are then irradiated through a structure template (mask to form the structure) and heated to create a difference in refractive index between the irradiated and non-irradiated parts of the composition with a varying refractive index.

In the above irradiation, an acid or a base is formed from the radiation-sensitive decomposing substance (C) to react with component (A) to decompose it. This decomposed product is distributed (dispersed) during the heating time after irradiation. As a result, there is a difference in refractive indices between the irradiated and non-irradiated parts.

During heating, the residual components (A) and (D), which did not react with the acid or base, interact with each other, stabilizing the resulting structure with a distribution of the refractive index.

The solvent used to obtain the solution containing the composition with a variable refractive index used in the present invention uniformly dissolves the above components (A), (B), (C), (D) and other optionally added additives and does not interact with these components.

Examples of the solvent include alcohols such as methanol, ethanol, propanol, isopropanol, 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; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate; propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and butylene propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone and

4-hydroxy-4-methyl-2-pentanone; esters such as 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, propillactate, butyl lactate,

methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate,

propyl 3-hydroxypropionate, butyl 3-hydroxypropionate,

methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate,

ethyl methoxy acetate, propyl methoxy acetate, butyl methoxy acetate, methylethoxy acetate, ethyl ethoxy acetate, propylethoxy acetate,

butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate,

propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate,

ethylbutoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate,

propyl 2-methoxypropionate, butyl 2-methoxypropionate,

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,

methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate,

propyl 3-ethoxypropionate, butyl 3-ethoxypropionate,

methyl 3-propoxypropionate, ethyl 3-propoxypropionate,

propyl 3-propoxypropionate, butyl 3-propoxypropionate,

methyl 3-butoxypropionate, ethyl 3-butoxypropionate,

propyl 3-butoxypropionate and butyl 3-butoxypropionate; and fluorine atom-containing solvents such as trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene,

hexafluorobenzene, hexafluorocyclohexane,

perfluorodimethylcyclohexane, perfluoromethylcyclohexane,

octafluorodecalin and 1,1,2-trichloro-1,2,2-trifluoroethane.

Among these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, ketones, esters and diethylene glycols are preferred in terms of solubility, reactivity of each component and ease of formation of a coating film.

In addition, a high boiling solvent can be used in combination with the above solvent. Examples of a high boiling solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide,

N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol,

benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,

γ-butyrolactone, ethylene carbonate, propylene carbonate and phenyl cellosolve acetate.

The composition with a variable refractive index used in the present invention is molded before exposure to it, giving it various shapes depending on the purpose of the application. For example, it is formed into a rod, fiber, long plate, sphere, film or lens, and the present invention is not limited to these forms. For molding a composition with a variable refractive index of the present invention, the commonly used method can be used. For example, injection molding, injection molding (direct compression), blow molding, extrusion, case polymerization, shewing (cutting), drawing or drawing, heating / cooling, CVD deposition (chemical vapor deposition, CVD), agglomeration or deployment are used . Also, in accordance with the purposes of using the optical molded product, centrifugal coating, longitudinal cutting, coating with excess removal using a strip, solvent distribution, LB, spraying, rolling coating, embossing or screen printing can be used.

With this molding method, heating is preferably carried out (hereinafter referred to as “pre-calcination”). Heating conditions that vary according to the composition of the material of the present invention and the type of each additive are preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C. For heating, you can use a hot plate or oven, or infrared radiation.

The radiation used for irradiation is an i-beam having a wavelength of 365 nm, an h-beam having a wavelength of 404 nm, a g-beam having a wavelength of 436 nm, an ultraviolet ray from light sources with a wide range of wavelengths, such like a xenon lamp, a far ultraviolet beam, such as a KrF excimer laser beam having a wavelength of 248 nm, or an ArF excimer laser beam having a wavelength of 193 nm, X-rays, such as synchrotron radiation, a charged particle stream, such as an electron beam, visible beam or them with Thou. Among them, ultraviolet radiation and visible radiation are preferred. Illumination, which depends on the wavelength of the radiation, is preferably from 0.1 to 100 mW / cm ² , since this achieves the highest reaction efficiency. The emission of radiation through the structure template makes it possible to form the necessary structure pattern from a radiation-sensitive material with a varying refractive index. Regarding the accuracy of the patterning of the structure, which depends on the light source used, an optical component having a variation in the distribution of the refractive index with a resolution of about 0.2 μm can be obtained using the present invention.

In the present invention, preferably after irradiation, heating is carried out (hereinafter referred to as “firing after irradiation” from English post-exposure baking, REV). For REV, you can use a device similar to the above for preliminary firing, and REV conditions can be arbitrary. The heating temperature is preferably from 30 to 150 ° C., More preferably from 30 to 130 ° C. Heating for the purpose of stabilization is preferably carried out sequentially after REV or separately from REV for the interaction of the residual components (A) and (D). The heating temperature for stabilization is preferably 35 to 200 ° C., more preferably the temperature is 10 or more degrees Celsius higher than the REV temperature, and even more preferably the temperature is 20 or more degrees higher than the REV temperature.

Then it can be re-irradiated to decompose the residual component (C) existing in the non-irradiated part, and to further improve the stability of the material.

Repeated irradiation can be carried out using radiation having the same wavelength as the radiation used to change the refractive index by exposing the entire surface of the structure as a whole in the same amount.

If necessary, the stability of the material can be further improved by heating. For heating, you can use a device similar to the device for pre-firing during molding of the material, and the heating conditions can be arbitrary.

In accordance with the present invention, the method of forming a structure with a distribution of the refractive index of the present invention can also be carried out by irradiating the radiation of a composition with a variable refractive index, including the above components (A), (B) and (C), through the template structure and treating it with a stabilizer (D).

The treatment with stabilizer (D) is preferably carried out after firing after irradiation, i.e. REAR

The function of the stabilizer (D) is to stabilize the residual degradable compound (A) contained in the material with a variable refractive index after irradiation to ensure stability to acid or base. Such stabilization prevents a change in the refractive index and, consequently, a deterioration in the quality of the structure with the distribution of the refractive index obtained by the method of the present invention, even when it is used under conditions in which the light transmitted through it has a wavelength close to the wavelength used to change the index refraction.

In addition to the above examples, low boiling compounds such as ammonia or triethylamine can be used as stabilizer (D).

Any suitable method can be used to contact between the stabilizer (D) and the composition with a variable refractive index after irradiation to stabilize it. For example, component (D) and, if necessary, the catalyst are dissolved in a suitable solvent for contacting the composition with a variable refractive index in the form of a solution. Alternatively, when component (D) in contacting conditions is a liquid or gas, it can be 100% directly in contact with a composition with a variable refractive index.

When a solvent is used in the reaction between the above stabilizer (D) and component (A), the solvent preferably dissolves component (D) and optionally added catalyst, but does not dissolve component (A). When choosing the above solvent, the surface of the obtained structure with a distribution of the refractive index will not become rough.

Examples of such a solvent include water, alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, tert-butanol, cyclohexanol, ethylene glycol, propylene glycol and diethylene glycol; ethers such as diethyl ether and 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; 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 alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and butylene propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane,

n-heptane and n-octane; ketones such as methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl amyl ketone and

4-hydroxy-4-methyl-2-pentanone; esters such as ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate,

methyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate,

butylhydroxyacetate, ethyl lactate, propillactate, butyl lactate, methyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, ethyl methoxy acetate, butyl methoxy acetate,

ethyl 2-methoxypropionate, butyl 2-methoxypropionate,

butyl-2-ethoxypropionate, butyl-2-butoxypropionate,

butyl 3-methoxypropionate, butyl 3-ethoxypropionate,

butyl 3-propoxypropionate and butyl 3-butoxypropionate; and fluorine atom-containing solvents such as trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene,

hexafluorobenzene, hexafluorocyclohexane,

perfluorodimethylcyclohexane, perfluoromethylcyclohexane,

octafluorodecalin and 1,1,2-trichloro-1,2,2-trifluoroethane.

Among these solvents, water, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, and fluorine-containing solvents are preferred.

The reaction temperature for the interaction between the stabilizer (D) and the residual degradable compound (A) is usually from 0 to 130 ^about C, and the reaction time is usually from 10 seconds to 1 hour.

In addition, re-irradiation can be carried out to decompose the residual component (C) existing in the non-irradiated part and further improve the stability of the material.

As for what was not described here when considering a method of forming a structure with a distribution of an indicator, including the above stabilization, it should be understood that the above description of a method of forming a structure with a distribution of a refractive index is applied directly or using modifications that are obvious to ordinary specialists in this areas of technology.

In addition, in accordance with the present invention, the method of forming a structure with a distribution of the refractive index can also be carried out by irradiating a composition with a variable refractive index, including the above components (A), (B) and (C), through a structure template and heating for decomposition the decomposable compound (A) in the non-irradiated portion.

The above heating is preferably performed at a temperature of 10 degrees Celsius or more higher than the PEB temperature, preferably at 170 ^C or higher, more preferably at 200 ^C or higher.

With the above heating, the residual degradable compound (A) existing in the non-irradiated part is removed by decomposition or sublimation and preferably does not substantially form pores.

As for what is not described here when considering a method of forming a structure with a distribution of the refractive index for the case when component (D) is not contained, it should be understood that the related paragraphs of the above description of the method of forming the structure are used directly or using modifications, obvious to ordinary specialists in this field of technology.

In the structure with the distribution of the refractive index of the present invention, which is obtained by any of the above various methods, the refractive index of the part that has been irradiated (first region) is preferably lower than the refractive index of the non-irradiated part (second region). Such a difference can be adjusted to a desired value by controlling the types and contents of components (A) and (B) contained in the variable refractive index composition used in the present invention. For example, the largest difference in refractive index can be set to a value in excess of 0.02.

The refractive index distribution structure of the present invention has pores or does not have any pores in the irradiated portion.

When the irradiated portion has pores, the porosity is preferably from 10 to 99.9%, more preferably from 15 to 99.9%, particularly preferably from 20 to 99.9%.

The elastic moduli of the irradiated and non-irradiated parts are preferably 0.3 GPa or more and 1 GPa or more, more preferably 0.5 GPa or more and 3 GPa or more, respectively.

The modulus of elasticity of the irradiated part is preferably less than the elastic modulus of the non-irradiated part.

Since the structure with the distribution of the refractive index of the present invention does not deteriorate, keeping the refractive index unchanged even when it is used under conditions of transmission through it of light having a wavelength close to the wavelength used to change the refractive index, as described above, it is especially useful as an optical material for use in the optoelectronic field and the field of display devices (displays).

Since the structure with the distribution of the refractive index of the present invention has a significantly more significant difference in the refractive index and the resulting difference in the refractive index is stable to light and heat, it is especially useful as an optical material for use in the optoelectronic region and the field of display devices. The refractive index distribution structure of the present invention can be used in optical parts, such as various optical sets, lenses, optocouplers, optical choppers, polarized beam splitters, holograms, single-mode and multimode optical fibers, fiber bundles or packets, optical fibers, single-core, multi-core and photoelectric optical communication connectors, optical isolators, polarizers, optical sensors such as photodiodes, phototransistors, photo-integral numerical schemes, CCD imaging devices (i.e. based on charge-coupled devices, from the English charge-coupled device), CMOS imaging devices (i.e. based on a complementary metal-oxide-semiconductor structure, CMOS), optical fiber sensors and fiber optic gyroscopes, optical discs such as CDs, i.e. CD, i.e. laser disc, PD i.e. rewritable disc with phase transition (from the English. phase-change dual or phase-dual) and DVD, i.e. digital universal disk (from the English digital versatile disk) optical switches, waveguides, optical touch panels (screens), diffraction gratings, optical guide rails, optical diffusion sensors, anti-reflectors and optical sealants.

The method of obtaining optical parts

Before irradiation, a photosensitive composition with a varying refractive index is formed into various shapes depending on the application.

For example, it is molded in the form of a rod, fiber, long plate, sphere, film or lens, and the present invention is not limited to these forms. For molding a composition with a variable refractive index, you can use the commonly used method, illustrated by injection molding, direct pressing, blow molding, extrusion, shell polymerization, shewing (cutting), drawing (drawing), heating / cooling, CVD deposition (chemical vapor deposition ), agglomeration or deployment. Also, in accordance with the purposes of using the optical molded product, centrifugal coating, longitudinal cutting, coating with excess removal using a strip, solvent distribution, LB, spraying, rolling coating, embossing or screen printing can be used.

The light used for irradiation is an i-ray having a wavelength of 365 nm, an h-ray having a wavelength of 404 nm, a g-ray having a wavelength of 436 nm, an ultraviolet ray from light sources with a wide range of wavelengths, such like a xenon lamp, a far ultraviolet beam, such as a KrF excimer laser beam having a wavelength of 248 nm, or an ArF excimer laser beam having a wavelength of 193 nm, X-rays, such as synchrotron radiation, a charged particle stream, such as an electron beam, visible beam or mixtures thereof. Among them, ultraviolet radiation and visible radiation are preferred. Illumination, which depends on the wavelength of the radiation, is preferably from 0.1 to 100 mW / cm ² , since this achieves the highest reaction efficiency. The emission of radiation through a structure template makes it possible to form a structure pattern from a radiation-sensitive material with a varying refractive index. Regarding the accuracy of the patterning of the structure, which depends on the light source used, an optical component having a variation in the distribution of the refractive index with a resolution of about 0.2 μm can be obtained using the present invention.

In the present invention, preferably after irradiation, heating is carried out (hereinafter referred to as “calcination after irradiation” and / or REV). The heating conditions, which vary according to the material composition of the present invention and the type of each additive is preferably 30 ^to 200 ° C, more preferably from 40 to 150 ° ^C can be used for heating a hot plate or oven, or infrared radiation.

The difference between the maximum refractive index and the minimum refractive index in the distribution of the refractive index of the optical part of the present invention can be set to the desired value in accordance with the application, as described above. It can be set at 0.02 or more, optionally 0.03 or more, 0.05 or more, or 0.08 or more.

As specific examples, methods for forming an optical fiber, lenses, optical waveguide, diffraction grating, holographic element and recording medium will be described in detail.

The method of forming an optical fiber

The optical fiber can be obtained by any suitable method, for example, by the following method.

A photosensitive composition with a variable refractive index for the formation of an optical fiber can be dissolved in a suitable solvent before use. The solvent used may be a solvent having a boiling point of from 50 to 200 ° C, and the solids content of the resulting solution may be from 50 to 80%. This solution is used as the initial solution for the fiber, is defoamed, stretched by heating, irradiated with a laser beam and extruded to form fiber. The pore diameter can be from 0.1 to 1.0 mm and the drawing speed can be from 0.1 to 1000 m / min.

The fiber obtained as described above is then uniformly irradiated from all sides with light toward the center using an annular light source with an optical fiber or reflector and fired after irradiation to obtain the optical fiber of the present invention. REV temperature can be from 50 to 200 ° C and the firing time can be from 1 second to 30 minutes. As a heating source, a suitable heating source, such as an infrared lamp, can be used.

A GI type optical fiber having such a distribution that the refractive index decreases in a parabolic manner from the central axis to the periphery can be formed by adjusting the amount of exposure, selecting a wavelength, and using an ultraviolet light absorber.

The aforementioned fiber drawing apparatus, an irradiation device, and a heating device may be adjacent. Thus, a GI type optical fiber can be produced continuously.

The method of forming lenses

The lenses of the present invention can be obtained by any suitable method, for example, the following method.

(1) a method for producing GRIN lenses having concave lens capabilities

The variable refractive index photosensitive composition used to form the lenses may be dissolved in a suitable solvent before use. The solvent used may be a solvent having a boiling point of from 50 to 200 ° C, and the solids content of the resulting solution may be from 50 to 80%. This solution is formed into a disk having the desired shape by hot pressing or the like.

After that, the disk is irradiated with light in such a way that the amount of radiation was greater in the central part of the disk and decreased to the periphery of the disk, and then burned after irradiation to obtain GRIN lenses with the possibility of concave lenses. The irradiation device is as shown in FIG.

The aperture 2, which can be opened or closed, is installed in the radiating device in figure 1 opposite the disk sample 1, and only parallel rays from the above light source are emitted to the sample when the closed aperture 2 is gradually opened, and the shutter speed is controlled so that the aperture 2 is completely open for a period of time from 1 second to 5 minutes to achieve the above exposure state.

Firing conditions after irradiation include a temperature of from 50 to 200 ° C and a time of from 1 second to 30 minutes.

(2) a method for forming GRIN lenses having convex lens capabilities

Similar to that described above in example (1), a disk sample is irradiated with light so that the amount of radiation is greater at the periphery of the disk and decreases toward the center of the disk, and then fired after irradiation to obtain GRIN lenses with convex lens capabilities.

Such an irradiation state can be obtained by applying light only from the side (side), while the upper part and the bottom of the cylinder are closed from light. An optical fiber or reflector can be used to evenly irradiate from the side.

You can use the same REV conditions as in (1) above.

The method of forming an optical waveguide

The optical waveguide of the present invention can be obtained by any suitable method, for example, the following method.

A photosensitive composition with a variable refractive index used to produce an optical waveguide can be dissolved in a suitable solvent before use (solution A). The solvent used may be a solvent having a boiling point of from 50 to 200 ° C, and the solids content of the resulting solution may be from 20 to 60%.

Separately from this solution, a composition solution is prepared containing component (B) and a thermal acid generator and / or acid photogenerator (solution B). The solids content in this solution can be from 20 to 60%, while you can use a solvent having a boiling point of from 50 to 200 ° C.

Solution B is first applied to any suitable substrate, such as a silicon substrate or a glass substrate, and then the solvent is removed to form a coating film with a thickness of 1 to 50 μm. This coating film serves as a layer of the lower shell. For applying the solution can be used coating by spin coating or slit coating, and the solvent may be removed by heating at 50-150 ^{° C} for 1-30 minutes.

After that, solution A, prepared as described above, is applied to the layer of the lower shell, and then the solvent is removed to form an intermediate layer with a thickness of 1 to 50 μm. The method of coating and removing the solvent may be the same as described above.

Subsequently, the intermediate layer is irradiated with light through a photomask to shield the central part (core) of the waveguide structure from light from light and is fired after irradiation. The non-irradiated portion serves as a central portion or core, and the irradiated portion acts as a side sheath layer. Firing conditions after irradiation include a temperature of from 50 to 200 ° C and a time of from 1 second to 30 minutes.

Solution B is again applied to the above intermediate layer, and then the solvent is removed to form a layer of the upper shell with a thickness of 1 to 50 microns, which makes it possible to obtain an optical waveguide. Since the obtained optical waveguide contains a thermal acid generator in the upper and lower shells, the acid formed to a small extent diffuses to the interface between the central layer (core) and the layer of the lower shell and between the central layer (core) and the layer of the upper shell. Thus, the interface between the Central layer and the shell layers can take such a structure that the refractive index gradually (gradient) changes in the upper, lateral and lower parts, resulting in a GI type optical waveguide.

The method of forming a recording medium

The recording medium of the present invention can be obtained by any suitable method, for example, the following method.

A photosensitive composition with a variable refractive index used to obtain a recording medium may be dissolved in a suitable solvent before use. The solvent used may be a solvent having a boiling point of from 50 to 200 ° C, and the solids content of the resulting solution may be from 5 to 50%.

This solution is applied to a flat plastic substrate having a metal film, such as an aluminum film with a thickness of about 60 nm, and then the solvent is removed to form a coating film with a thickness of 0.1 to 10 μm. Centrifugal coating or crevice coating can be used to apply the solution, and the solvent can be removed by heating at 50-150 ° C. for 1-30 minutes.

Then, this coating film is irradiated with light through a photomask having pointing tracks (tracks) 1.6 μm wide at a step of 0.2 to 0.5 μm, and fired after irradiation with the formation of an optical recording medium. Firing conditions after irradiation include a temperature of 50 to 200 ° C. and a time of 1 second to 30 minutes.

The method of forming a diffraction grating

The diffraction grating of the present invention can be obtained by any suitable method, for example, by the following method.

A photosensitive composition with a variable refractive index used to produce a diffraction grating can be dissolved in a suitable solvent before use. The solvent used may be a solvent having a boiling point of from 50 to 200 ° C, and the solids content of the resulting solution may be from 20 to 60%.

This solution is applied to the surface of a suitable substrate or substrate 6 (see FIG. 2), such as a glass substrate, and then the solvent is removed to form a thin coating film 5 with a thickness of 1 to 50 μm. Centrifugal coating or crevice coating can be used to apply the solution, and the solvent can be removed by heating at 50-150 ° C. for 1-30 minutes.

This coating film is irradiated with slit light and fired after irradiation to form a diffraction grating. For emitting light slit-like appearance, you can use the device and method shown, for example, in figure 2. Figure 2 shows that parallel rays 9 from the irradiating device 8, reflected using an obliquely mounted reflector 7, are emitted onto the coating film 5. Thus, the coating film is irradiated by an interference pattern formed by direct rays and reflected rays 9. The sample is moved in the shown in the figure, the direction of the arrow at a speed of 0.1-100 μm / min, while it is illuminated with the formation of a diffraction grating having the desired cycle of 0.3 μm or more. In this way, a highly accurate refractive index distribution can be created.

Another method for emitting slit-like light is by irradiating the coating film obtained as described above with a plurality of radial rays from various directions for interference, or by irradiating light through slits. In each of the methods, by changing the angle of the incoming light or the angle of the mirror, a diffraction grating having the desired cycle can be formed.

Firing conditions after irradiation include a temperature of from 50 to 200 ° C and a time of from 1 second to 30 minutes.

The method of forming a holographic element

The holographic element of the present invention can be obtained by any suitable method, for example, the following method.

A photosensitive composition with a variable refractive index used to form a holographic element can be dissolved in a suitable solvent before use. The solvent used may be a solvent having a boiling point of from 50 to 200 ° C, and the solids content of the resulting solution may be from 20 to 60%.

This solution is applied to any suitable substrate, such as a glass substrate, and then the solvent is removed to form a thin film with a thickness of 1 to 50 μm. Centrifugal coating or crevice coating can be used to apply the solution, and the solvent can be removed by heating at 50-150 ° C. for 1-30 minutes.

This coating film is irradiated with an interference pattern and fired after irradiation to form a recording medium (hologram) for holography. That is, the signal light passing through an object or material intended for recording and the reference light directly obtained from the same light source interfere with each other and are emitted onto the coating film to change the refractive index, thereby making it possible to record an image of this object or material on the covering film.

The above firing conditions after irradiation include a temperature of 50 to 200 ° C. and a time of 1 second to 30 minutes.

Examples

The following examples are provided to further illustrate the present invention, but should not be construed as limiting the invention.

The weight average molecular weight in polystyrene units was measured using Showa Denko K.K. GPC (gel permeation) chromatography system.

Examples 1-16 of the synthesis of component (A)

Example 1

50 parts by weight of o-phthalaldehyde as a monomer and 500 parts by weight of tetrahydrofuran were loaded into a 1 liter flask, the atmosphere inside of which was replaced with nitrogen, and cooled to -78 ° C. To this flask was added 1.0 part by weight of a solution of n-butyllithium in n-hexane (1.5 mol / liter) and stirred under cooling at –78 ° C for 48 hours in a nitrogen atmosphere.

While cooling, 0.8 parts by weight of acetic anhydride and 0.6 parts by weight of pyridine were added to the resulting reaction solution, and stirred at –78 ° C for 2 hours. The reaction solution was concentrated to 100 ml with heating at 60 ° C under reduced pressure and introduced into 5 liters of ion-exchanged water for 10 minutes. The precipitate was redissolved in 50 parts by weight of tetrahydrofuran, purified by re-precipitation with 5 liters of ion exchange resin and dried under vacuum at 50 ° ^C, yielding 45 parts by weight of compound (A-1). The weight average molecular weight of the obtained compound was 26,000.

Example 2

45 parts by weight of o-phthalic aldehyde, 5 parts by weight of benzaldehyde as monomers and 500 parts by weight of tetrahydrofuran were charged into a 1 liter flask, the atmosphere of which was replaced with nitrogen, and cooled to -78 ° C. To this flask was added 1.0 part by weight of a solution of n-butyllithium in n-hexane (1.5 mol / liter) and stirred while cooling at

–78 ° C for 48 hours in a nitrogen atmosphere.

While cooling, 0.8 parts by weight of acetic anhydride and 0.6 parts by weight of pyridine were added to the resulting reaction solution, and stirred at –78 ° C for 2 hours. The entire reaction solution was concentrated to 100 ml with heating at 60 ° C under reduced pressure and continuously introduced into 5 liters of ion-exchanged water for 10 minutes. The precipitate formed was redissolved in 50 parts by weight of tetrahydrofuran, purified by reprecipitation in 5 liters of ion exchange resin and dried in vacuum at 50 ° C to obtain 43 parts by weight of compound (A-2). The weight average molecular weight of the obtained compound was 15,000.

Example 3

45 parts by weight of o-phthalaldehyde, 5 parts by weight of glutaraldehyde as monomers and 500 parts by weight of tetrahydrofuran were charged into a 1 liter flask, the atmosphere inside of which was replaced with nitrogen, and cooled to -78 ° C. To this flask was added 1.0 part by weight of a solution of n-butyllithium in n-hexane (1.5 mol / liter) and stirred while cooling at

–78 ° C for 48 hours in a nitrogen atmosphere.

While cooling, 0.8 parts by weight of acetic anhydride and 0.6 parts by weight of pyridine were added to the resulting reaction solution, and stirred at –78 ° C for 2 hours. The entire reaction solution was concentrated to 100 ml with heating at 60 ° C under reduced pressure and continuously introduced into 5 liters of ion-exchanged water for 10 minutes. The precipitate formed was redissolved in 50 parts by weight of tetrahydrofuran, purified by reprecipitation in 5 liters of ion exchange resin and dried in vacuum 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.

Example 4

25 parts by weight of 4-chloro-o-phthalaldehyde as a monomer and 500 parts by weight of methylene chloride were charged into a 1 liter flask, the atmosphere of which was replaced with nitrogen, and cooled to -78 ° C. To this flask was added 0.1 part by weight of a complex of boron trifluoride with ether and stirred while cooling at –78 ° C for

48 hours under nitrogen.

While cooling, 0.8 parts by weight of acetic anhydride and 0.6 parts by weight of pyridine were added to the resulting reaction solution, and stirred at –78 ° C for 2 hours. The entire reaction solution was concentrated to 50 ml with heating at 60 ° C under reduced pressure and continuously introduced into 3 liters of ion-exchanged water for 5 minutes. The precipitate formed was redissolved in 30 parts by weight of tetrahydrofuran, purified by reprecipitation in 3 liters of ion exchange resin and dried in vacuum at 50 ° C to obtain 46 parts by weight of compound (A-4). The weight average molecular weight of the obtained compound was 48,000.

Example 5

25 parts by weight of 4-bromo-o-phthalaldehyde as a monomer and 500 parts by weight of methylene chloride were charged into a 1 liter flask, the atmosphere inside of which was replaced with nitrogen, and cooled to -78 ° C. To this flask was added 0.1 part by weight of a complex of boron trifluoride with ether and stirred under cooling at –78 ° C for 48 hours in a nitrogen atmosphere.

While cooling, 0.8 parts by weight of acetic anhydride and 0.6 parts by weight of pyridine were added to the resulting reaction solution, and stirred at –78 ° C for 2 hours. The entire reaction solution was concentrated to 50 ml with heating at 60 ° C under reduced pressure and continuously introduced into 3 liters of ion-exchanged water for 5 minutes. The precipitate was re-dissolved in 30 parts by weight of tetrahydrofuran, purified by re-precipitation in 3 liters of ion exchange resin and dried in vacuum 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.

Example 6

50 parts by weight of o-phthalaldehyde as a monomer and 500 parts by weight of tetrahydrofuran were loaded into a 1 liter flask, the atmosphere inside of which was replaced with nitrogen, and cooled to -78 ° C. 0.2 parts by weight of a solution of n-butyllithium in n-hexane (1.5 mol / liter) was added to this flask and stirred under cooling at –78 ° C for 48 hours in a nitrogen atmosphere.

While cooling, 0.8 parts by weight of acetic anhydride and 0.6 parts by weight of pyridine were added to the resulting reaction solution, and stirred at –78 ° C for 2 hours. The entire reaction solution was concentrated to 100 ml with heating at 60 ° C under reduced pressure and continuously introduced into 5 liters of ion-exchanged water for 10 minutes. The precipitate was redissolved in 50 parts by weight of tetrahydrofuran, purified by re-precipitation with 5 liters of ion exchange resin and dried under vacuum at 50 ^C to give 45 g of compound (A-6). The weight average molecular weight of the obtained compound was 110,000.

Example 7

33.05 g of 1,4-benzenethiol and 66.06 g of 1,4-di (2-nitrovinyl) benzene were dissolved in 100 g of N-methylpyrrolidone in a 500 ml three-necked flask under argon atmosphere. While cooling with ice and stirring for 1 hour, the solution obtained by dissolving 1.55 g was added to the above solution

N-methylmorpholine in 10 g of N-methylpyrrolidone. At the end of administration, the reaction solution was left at room temperature for 24 hours to effect polymerization. At the end of the polymerization, the obtained polymer was purified by reprecipitation from a mixture of tetrahydrofuran-methanol twice.

The precipitated polymer was separated by filtration and dried in vacuo at 50 ° C to obtain 72.80 g of compound (A-7). The weight average molecular weight of the obtained compound was 5800.

Example 8

49.84 g of terephthalic acid chloride was dissolved in 150 ml of chloroform in a 500 ml three-necked flask in an argon atmosphere. To the above solution was added a solution obtained by dissolving 33.05 g of 1,4-benzenethiol and 16.83 g of potassium hydroxide in 150 ml of ion-exchanged water, and stirred to effect interfacial polycondensation. After reaction for 6 hours, the obtained polymer was purified by reprecipitation twice from a mixture of tetrahydrofuran-methanol.

The precipitated polymer was separated by filtration and dried in vacuo at 50 ° C to obtain 61.28 g of compound (A-8). The weight average molecular weight of the obtained compound was 27600.

Example 9

33.05 g of 1,4-benzenethiol, 48.04 g of p-phenylenediisocyanate and 12 g of dibutyltin dichloride as a catalyst were dissolved in 200 ml of dimethyl sulfoxide in a 500 ml three-necked flask under argon atmosphere. At the end of the introduction, the reaction solution was heated at 60 ° C for 24 hours to effect polymerization. At the end of the polymerization, the obtained polymer was purified by reprecipitation from a mixture of tetrahydrofuran-methanol twice. The precipitated polymer was separated by filtration and dried in vacuo at 50 ° C to obtain 66.50 g of compound (A-9). The weight average molecular weight of the obtained compound was 15,000.

Example 10

92.42 g of 4-nitro-1,3-phenylene dichloroformate was dissolved in 400 ml of chloroform in a 1-l three-necked flask in an argon atmosphere. To the above solution was added a solution obtained by dissolving 33.05 g of 1,4-benzenethiol and 16.83 g of potassium hydroxide in 200 ml of ion-exchanged water and stirred to effect interfacial polycondensation. After reaction for 6 hours, the obtained polymer was purified by reprecipitation twice from a mixture of tetrahydrofuran-methanol.

The precipitated polymer was separated by filtration and dried in vacuo at 50 ° C to obtain 83.61 g of compound (A-10). The weight average molecular weight of the obtained compound was 32,000.

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 argon atmosphere. Under stirring and ice-cooling, the solution obtained by dissolving 23.73 g of pyridine in 50 g of N-methylpyrrolidone was added to the above solution for 1 hour. At the end of the introduction, the reaction solution was heated at 60 ° C for 24 hours to effect polymerization. At the end of the polymerization, the reaction solution was poured into 2 liters of methanol to precipitate and the residue was re-dissolved in 200 ml

N-methylpyrrolidone and introduced into 2 liters of methanol for purification by reprecipitation.

The precipitated polymer was separated by filtration and dried in vacuo at 50 ^C to give 70.80 g of the compound (A-11). The weight average molecular weight of the obtained compound was 26,000.

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 argon atmosphere. To the above solution was added a solution obtained by dissolving 0.06 g of p-toluenesulfonic acid in 10 g of diethylene glycol ethyl methyl ether and stirred for polymerization at ¹⁰⁰ ° C for 8 hours and then at 130 ° C for 1 hour. The polymerization was carried out until the methanol formed during the reaction was distilled off under reduced pressure.

At the end of the polymerization, the reaction solution was poured into 2 liters of methanol for precipitation, and the residue was redissolved in 100 ml of diethylene glycol ethyl methyl ether and introduced into 2 liters of methanol for purification by reprecipitation. The precipitated polymer was separated by filtration and dried in vacuo at 50 ° C to obtain 47.93 g of compound (A-12). The weight average molecular weight of the obtained compound was 5800.

Example 13

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 argon atmosphere. The solution obtained by dissolving 47.46 g of pyridine in 50 g of N-methylpyrrolidone was introduced into the above solution with stirring and cooling with ice for 1 hour. At the end of the introduction, the reaction solution was heated at 60 ° C for 24 hours to effect polymerization. At the end of the polymerization, the reaction solution was poured into 2 liters of methanol to precipitate and the residue was re-dissolved in 200 ml

N-methylpyrrolidone and introduced into 2 liters of methanol for purification by reprecipitation.

The precipitated polymer was separated by filtration and dried in vacuo at 50 ^C to give 80.01 g of the compound (A-13). The weight average molecular weight of the obtained compound was 31,200.

Example 14

61.51 g of terephthalic acid chloride was dissolved in 150 ml of chloroform in a three-neck flask with a capacity of 500 ml in an argon atmosphere. To the above solution was added a solution obtained by dissolving 33.05 g of 1,4-benzenethiol and 33.66 g of potassium hydroxide in 150 ml of ion-exchanged water, and stirred to effect interfacial polycondensation. After reaction for 6 hours, the obtained polymer was purified by reprecipitation twice from a mixture of tetrahydrofuran-methanol.

The precipitated polymer was separated by filtration and dried in vacuo at 50 ° C to obtain 75.98 g of compound (A-14). The weight average molecular weight of the obtained compound was 33600.

Example 15

50 g of o-phthalaldehyde as a monomer and 500 g of tetrahydrofuran were charged into a 1 liter flask, the atmosphere inside of which was replaced with nitrogen, and cooled to -78 ° C. To the above solution, 41.83 g of potassium tert-butoxide was added and stirred under cooling at –78 ° C. for 48 hours under a nitrogen atmosphere.

While cooling, 45.67 g of acetic anhydride and 35.38 g of pyridine were added to the obtained reaction solution, and they were stirred at –78 ° С for 2 hours. The reaction solution was concentrated to 100 ml with heating at 60 ° C, dissolved in 1 liter of ethyl acetate, washed three times with ion-exchanged water and dried in vacuum at 50 ° C after concentration of ethyl acetate, to obtain 45 g of compound (A-15). The initiator / monomer ratio in the obtained compound (A-15) was 1: 1 based on the integrated intensity of tert-butyl group protons obtained at 1.2-1.3 ppm. (ppm), and aromatic protons obtained at 7.2-7.7 ppm, measured using ¹ H NMR.

Example 16

49.84 g of terephthalic acid chloride was dissolved in 150 ml of chloroform in a 500 ml three-necked flask in an argon atmosphere. To the above solution was added a solution obtained by dissolving 33.05 g of 1,4-benzenethiol and 16.83 g of potassium hydroxide in 150 ml of ion-exchanged water, and stirred to effect interfacial polycondensation. After interaction for 4 hours, the obtained polymer was purified by reprecipitation twice from a mixture of tetrahydrofuran-methanol.

The precipitated polymer was separated by filtration and dried in vacuo at 50 ° C to obtain 56.55 g of compound (A-16). The weight average molecular weight of the obtained compound was 7600.

Examples 17-20 of the synthesis of component (B)

Example 17

15.22 g of tetramethoxysilane and 27.24 g of methyltrimethoxysilane were dissolved in 100 g of ethylene glycol ethyl methyl ether in a 1 liter three-necked flask, and the resulting mixture solution was heated at 60 ° C. with stirring using a magnetic stirrer. 5.20 g of ion-exchange water was continuously added to the mixture solution over 1 hour. After 4 hours at 60 ° C., the resulting reaction solution was cooled to room temperature. Then, 9.20 g of methanol, a by-product of the reaction, was distilled off under reduced pressure from the reaction solution. The solid content of the solution of the obtained polymer (B-1) was 33.2%, and the weight average molecular weight of the polymer was 2200.

Example 18

After completely replacing the atmosphere of a 1.5-liter steel autoclave equipped with an electromagnetic stirrer, 500 g of ethyl acetate, 57.2 g of ethyl vinyl ether (EVE), 10.2 g of hydroxybutyl vinyl ether (HBVE) and 3 g were loaded into nitrogen in an autoclave lauryl peroxide and cooled to –50 ° C using dry ice and methanol, and oxygen in the system was again removed using nitrogen gas. Hexafluoropropylene (HFP) was then charged and the temperature began to rise. The pressure at the moment when the internal temperature in the autoclave reached 60 ° C was 5.3 kgf / cm ² . Then the interaction was continued at 60 ° C for 20 hours with stirring and the autoclave was cooled with water when the pressure dropped to 1.5 kgf / cm ² to stop the reaction. After reaching room temperature, unreacted monomers were discarded and the autoclave was opened to give a polymer solution having a solids content of 28.1%. The resulting polymer solution was introduced into methanol to precipitate a polymer, which was then washed with methanol and dried in vacuo at 50 ° C to obtain 193 g of a fluorine-containing copolymer. The weight average molecular weight of the obtained polymer (B-2) was 17,000.

Example 19

8 g of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 g of diethylene glycol dimethyl ether were charged into a 500 ml three-necked flask. Then, 20 g of methacrylic acid, 30 g of glycidyl methacrylate and 50 g of pentafluoroethyl methacrylate were loaded into the flask, the internal atmosphere in the flask was replaced with nitrogen, and stirring was carefully started. The temperature of the solution was raised to 70 ° C and kept at this temperature for 3 hours to obtain a polymer solution (B-3). The solid content of the obtained polymer solution was 31.0%, and the weight average molecular weight of the polymer was 12000.

Example 20

50 g of methyltrimethoxysilane was charged into a 1 liter three-necked flask, 100 g of 1-ethoxy-2-propanol was added and dissolved in methyltrimethoxysilane, the resulting solution was heated at 60 ° C with stirring using a magnetic stirrer. To this solution, 19.85 g of ion exchange water was continuously added over 1 hour. The interaction was carried out at 60 ° C for 4 hours and the resulting reaction solution was cooled to room temperature.

Then, methanol, a by-product of the reaction, was distilled off from the reaction solution under reduced pressure, and the reaction solution was concentrated to a solids content of 20% by weight to obtain a solution containing compound (B-4). The weight average molecular weight of compound (B-4) was 8000.

Example 21

40 parts by weight of compound (A-1) as component (A), 60 parts by weight of co-condensate (molecular weight 2000) of a mixture of methyltrimethoxysilane and tetramethoxysilane (weight ratio 55: 5) as component (B) and 1 part by weight 2 - (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine as component (C) was dissolved in diethylene glycol ethyl ether to a total solids content of 20 wt.%, And the resulting solution was filtered through a membrane filter having a diameter pore 0.2 μm, to obtain a solution containing a photosensitive th composition with a variable refractive index.

The formation of a coating film

The above solution was applied to a silicon substrate using a die and preliminarily fired on a hot plate at 90 ° C for 2 minutes to form a coating film with a thickness of 1.0 μm.

Irradiation

The resulting coating film was irradiated with 20 mJ / cm ² at the optimum focusing depth using a projection exposure device with image reduction NSR1506i6A (Nikon Corporation, NA = 0.45, λ = 365 nm) to create a difference in the refractive index between the exposed and unexposed irradiation with parts of a composition with a variable refractive index. Then, the coating film was fired after irradiation on a hot plate at 120 ° C. for 2 minutes

Refractive index measurement

The refractive indices of the exposed and non-irradiated parts of the silicon substrate were measured at room temperature at 633 nm using an Auto EL IV NIR III ellipsometer (Rudolf Research Co., Ltd). The results are presented in table 1.

Transparency rating

A glass substrate coated with a photosensitive composition with a variable refractive index was obtained in the same manner as above, except that instead of a silicon substrate, a Corning 1737 glass substrate was used (Corning Co., Ltd.).

Then, the optical permeability of the obtained glass substrate was measured at a wavelength of 400 to 800 nm using a 150-20 double-beam spectrophotometer (Hitachi, Ltd.). We can say that when the minimum optical permeability exceeded 95%, the optical permeability is satisfactory, and when the minimum optical permeability is 95% or less, the optical permeability is unsatisfactory. The results are presented in table 1.

Example 22

The procedure of Example 21 was repeated except that the amount of irradiation was changed to 300 mJ / cm ² to evaluate the refractive index and transparency. The results are presented in table 1.

Example 23

The evaluation was carried out in the same manner as in Example 21, except that 70 parts by weight of compound (A-1) were used as component (A), and 30 parts by weight of methyltrimethoxysilane condensate (molecular weight 2000) was used as component (IN). The results are presented in table 1.

Example 24

The evaluation was carried out in the same manner as in Example 21, except that 15 parts by weight of compound (A-1) were used as component (A), and 85 parts by weight of methyltrimethoxysilane condensate (molecular weight 2000) was used as component (IN). The results are presented in table 1.

Example 25

The evaluation was carried out in the same manner as in Example 21, except that 40 parts by weight of compound (A-2) was used as component (A). The results are presented in table 1.

Example 26

The evaluation was carried out in the same manner as in Example 21, except that 40 parts by weight of compound (A-3) was used as component (A). The results are presented in table 1.

Example 27

The evaluation was carried out in the same manner as in Example 21, except that 40 parts by weight of compound (A-4) was used as component (A). The results are presented in table 1.

Example 28

The evaluation was carried out in the same manner as in Example 21, except that 40 parts by weight of compound (A-5) was used as component (A). The results are presented in table 1.

Example 29

The evaluation was carried out in the same manner as in Example 21, except that 1 part by weight of 4-phenylthiophenyl diphenylsulfonium trifluoromethanesulfonate was used as component (C). The results are presented in table 1.

Example 30

The evaluation was carried out in the same manner as in Example 21, except that 1 part by weight of diphenyl iodonium trifluoroacetate was used as component (C). The results are presented in table 1.

Table 1 Example The amount of irradiation mJ / cm2 Refractive index Transparency Irradiated
part Non-irradiated part I will-
melting irradiation part
(%) Non-irradiated part
(%) Example 21 20 1.42 1,52 99.3 99.0 Example 22 300 1.42 1,52 99.3 99.0 Example 23 20 1.42 1.55 99.5 98.6 Example 24 20 1.42 1.47 99,2 99.1 Example 25 20 1.42 1,52 99.3 99.1 Example 26 20 1.42 1.51 99.3 99,2 Example 27 20 1.42 1,53 99.3 99.0 Example 28 20 1.42 1,56 99.3 98.6 Example 29 20 1.42 1,52 99.3 99.0 Example 30 20 1.42 1,52 99.3 99.0

Example 31

50 parts by weight of compound (A-7) as component (A), 50 parts by weight of polymer (B-1) as component (B) and 5 parts by weight of 2-benzyl-2-dimethylamino-1- (morpholinophenyl ) -butan-1-one as component (C) was dissolved in diethylene glycol ethyl methyl ether to a total solids content of 20% and the resulting solution was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a solution of the composition.

The formation of a coating film, a measurement of the refractive index, and transparency were performed in the same manner as in Example 21.

Irradiation and Roar

The resulting coating film was irradiated at an optimal focusing depth using a projection exposure device with image reduction NSR1506i6A (Nikon Corporation, NA = 0.45, λ = 365 nm). Firing after irradiation (REV) was performed for 2 minutes to create a difference in the refractive index between the exposed and non-irradiated parts of the composition with a variable refractive index. The amount of exposure and the temperature of the REV are shown in table 2.

Example 32

The evaluation was carried out in the same manner as in Example 31, except that 50 parts by weight of compound (A-8) was used as component (A). The results are presented in table 2.

Example 33

The evaluation was carried out in the same manner as in Example 31, except that 50 parts by weight of compound (A-9) was used as component (A). The results are presented in table 2.

Example 34

The evaluation was carried out in the same manner as in Example 31, except that 50 parts by weight of compound (A-10) was used as component (A). The results are presented in table 2.

Example 35

The evaluation was carried out in the same manner as in Example 31, except that 50 parts by weight of compound (B-2) was used as component (B). The results are presented in table 2.

Example 36

The evaluation was carried out in the same manner as in Example 31, except that 50 parts by weight of compound (B-3) was used as component (B). The results are presented in table 2.

table 2 Example The amount of irradiation (mJ / cm2) Roar temperature
(° C) Refractive index Transparency Exposed Part Non-irradiated part Irradiated portion (%) Not exposed
Irradiated part
(%) Example 31 80 130 1.42 1.55 99.3 99.0 Example 32 80 130 1.42 1,58 98.9 98.6 Example 33 80 130 1.42 1,57 99.1 98.9 Example 34 80 130 1.42 1,56 99,2 99.0 Example 35 80 130 1.38 1,52 99.3 99.1 Example 36 80 130 1.42 1.55 99.3 99.1 Example 31 130 130 1.42 1.55 99.3 99.0 Example 31 150 100 1.42 1.55 99.3 99.0

Example 37

50 parts by weight of compound (A-11) as component (A), 50 parts by weight of a solution containing polymer (B-1), as component (B) (equivalent to 50 parts by weight (solids content) of the polymer ( B-1)) and 1 part by weight of 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine as component (C) was dissolved in diethylene glycol ethyl ether to a total solids content of 20% , and the resulting solution was filtered through a membrane filter having a pore diameter of 0.2 μm, to obtain a solution of the composition with a variable display refractive elem.

(1) coating film formation

The above solution was applied to a silicon substrate using a die and preliminarily fired on a hot plate at 90 ° C for 2 minutes to form a coating film with a thickness of 1.0 μm.

(2) structure formation with a distribution of refractive index

The coating film obtained as described above was irradiated with 50 mJ / cm ² at an optimal focusing depth using a projection exposure device with image reduction NSR1505i6A (Nikon Corporation, NA = 0.45, λ = 365 nm). Then, the coating film was fired after irradiation at 130 ° C. for 2 minutes to form a difference in refractive index between the exposed and non-irradiated parts. As for the resulting structure with a distribution of the refractive index, the irradiated part will be referred to hereinafter as the “low refractive index” part, and the non-irradiated part will be referred to hereinafter as the “high refractive index part".

(3) refractive index measurement

The refractive indices of the low refractive index part and the high refractive index part obtained according to the above-described structure with a refractive index distribution were measured at 633 nm using an Auto EL IV NIR III ellipsometer (Rudolf Research Co., Ltd). The results are presented in table 3.

(4) transparency assessment

A structure with a refractive index distribution was obtained on a glass substrate in the same manner as described in (1) and (2), except that instead of a silicon substrate, a Corning 1737 glass substrate was used (Corning Co., Ltd.). Also hereinafter, the irradiated portion of the refractive index distribution structure formed on the glass substrate will be referred to as the “low refractive index portion”, and the non-irradiated portion will be referred to as the “high refractive index portion”.

Then, the optical permeability of the low refractive index part and the high refractive index part of a glass substrate having such a structure with a refractive index distribution was measured using a 150-20 double beam spectrophotometer (Hitachi, Ltd.) at a wavelength of 400 to 800 nm. We can say that when the minimum optical permeability exceeded 95%, then the optical permeability is satisfactory, and when the minimum optical permeability is 95% or less, the optical permeability is unsatisfactory. The results are presented in table 3.

(5) stabilization

150 ml of phenyl glycidyl ether (containing 0.1 mmol tetrabutylammonium bromide as a reaction catalyst) as a component (D) was heated to 100 ° C, and the refractive index distribution structures obtained on the silicon substrate and glass substrate as described above were immersed in phenyl glycidyl ether at 100 ° C for 2 minutes and washed with super pure water for 1 minute.

Then, the entire surface of the structures was re-irradiated at 4.5 mW / cm ² using a Canon PLA-501F without a filter for 1 minute and heated in an oven at 200 ° C for 10 minutes to stabilize the structures with a refractive index distribution.

(6) refractive index and transparency assessment

The refractive indices of the low refractive index part and the high refractive index part of the above stabilized structure with the distribution of the refractive index obtained on the silicon substrate were measured in the same manner as described in (3) above. The results are presented in table 4.

The transparency of the low refractive index part and the high refractive index part of the above stabilized structure with the distribution of the refractive index obtained on the glass substrate was measured in the same manner as described in (4) above. The results are presented in table 4.

(7) assessment of the stability of the structure with a distribution of the refractive index

The entire surface of the above stabilized structure with a refractive index distribution obtained on a silicon substrate, and the entire surface of the above structure with a refractive index distribution obtained on a glass substrate, was subjected to irradiation at 4.5 mW / cm ² for 30 minutes using Canon PLA- 501F without filter to accelerate exposure.

The refractive indices of the low refractive index part and the high refractive index part of the thus treated structure with the distribution of the refractive index obtained on the silicon substrate were measured in the same manner as in (3) above. The results are presented in table 4.

The transparency of the low refractive index part and the high refractive index part of the stabilized structure with the distribution of the refractive index obtained on the glass substrate was measured in the same manner as in (4) above. The results are presented in table 4.

Example 38

The estimates were carried out in the same manner as in Example 37, except that 50 parts by weight of the compound (A-12) were used as component (A), the temperature of the REV in step (2) (structure formation with a distribution of the refractive index) was changed as shown in table 3, and the type of component (D) and the stabilization temperature in step (5) (stabilization) were changed as shown in table 4. The results are presented in table 3 and table 4.

Example 39

Estimates were carried out in the same manner as in Example 37, except that 50 parts by weight of compound (A-1) were used as component (A), the exposure value in step (2) (structure formation with a refractive index distribution) was changed as shown in table 3, and the type of component (D) and the stabilization temperature in step (5) (stabilization) were changed as shown in table 4. The results are presented in table 3 and table 4.

Example 40

Evaluation was carried out in the same manner as in Example 37, except that 50 parts by weight of compound (A-8) was used as component (A), 5 parts by weight of N- (2-nitrobenzyloxycarbonyl) pyrrolidine was used as component (C), the exposure value in step (2) (formation of a structure with a refractive index distribution) was changed as shown in table 3, and the type of component (D) in step (5) (stabilization) was changed as shown in table 4. Results presented in table 3 and table 4.

Example 41

The evaluations were carried out in the same manner as in Example 37, except that a solution containing polymer (B-2) (equivalent to 50 parts by weight (solids content) of polymer (B-2) was used as component (B) The results are presented in table 3 and table 4.

Example 42

The evaluations were carried out in the same manner as in Example 37, except that 1 part by weight of 4-phenylthiophenyl diphenylsulfonium trifluoromethanesulfonate was used as component (C) and the exposure value in step (2) (structure formation with refractive index distribution) was changed as shown in table 3. The results are presented in table 3 and table 4.

Example 43

Estimates were carried out in the same manner as in Example 40, except that the exposure value at stage (2) (structure formation with a refractive index distribution) was changed as shown in Table 3. The results are presented in Table 3 and Table 4.

Table 3 Example Formation Conditions
refractive index distribution structures Optical properties before stabilization Refractive index Transparency Value
exposure
(mJ / cm²) REV temperature
Rutra (° C)
Low Refractive Part High Refractive Part Low part
Indicator
refraction (%) High part
indicator
refraction (%)
Example 37 fifty 130 1.42 1,53 99.3 99.0 Example 38 fifty 120 1.42 1.55 99.3 98.6 Example 39 20 130 1.42 1,52 99.3 99.0 Example 40 80 130 1.42 1,58 98.9 98.6 Example 41 fifty 130 1.42 1,52 99.3 99.1 Example 42 40 130 1.42 1,53 99.3 99.0 Example 43 90 130 1.42 1,58 98.9 98.6

Example Stabilization conditions Optical properties after stabilization Refractive index Transparency Component Type
(D) Temperature
(° C) Low part
refractive index High Refractive Part Low part
Refractive index (%) Part with a high refractive index (%) Example 37 D-1 100 1.42 1,54 99.3 99.0 Example 38 D-2 20 1.42 1.55 99.3 98.7 Example 39 D-2 20 1.42 1,54 99.3 99.0 Example 40 D-3 100 1.42 1,58 98.9 98.6 Example 41 D-1 100 1.42 1,54 99.3 99.1 Example 42 D-1 100 1.42 1,54 99.3 99.0 Example 43 D-3 100 1.42 1,58 98.9 98.6

Table 4
Example Optical properties after accelerated exposure Refractive index Transparency Low part
refractive index High part
refractive index Low part
refractive index (%) High part
refractive index (%) Example 37 1.42 1,54 99.3 99.0 Example 38 1.42 1.55 99.3 98.7 Example 39 1.42 1,54 99.3 99.0 Example 40 1.42 1,58 98.9 98.6 Example 41 1.42 1,54 99.3 99.1 Example 42 1.42 1,54 99.3 99.0 Example 43 1.42 1,58 98.9 98.6

In table 4, the symbols for component (D) denote the following: D-1 - phenyl glycidyl ether (containing 10 mol.% Tetrabutylammonium bromide); D-2 - 1% aqueous solution of p-xylylenediamine; D-3 - 3-phenoxypropylene sulfide (containing 10 mol.% Tetrabutylammonium bromide)

Example 44

50 parts by weight of compound (A-11) as component (A), a solution containing polymer (B-1) (equivalent to 50 parts by weight (solids content) of polymer (B-1)), as component (B) , 1 part by weight of 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine as component (C) and 10 parts by weight of diglycidyl ether of bisphenol A as component (D) was dissolved in ethyl methyl diethylene glycol ether to a total solids content of 20%, and the resulting solution was filtered through a membrane filter having a diameter p p 0.2 micron, to obtain a composition solution having a varying refractive index.

Obtaining a coating film, forming a structure with a distribution of the refractive index, measuring the refractive index, evaluating the transparency and evaluating the refractive index and transparency were carried out in the same manner as in example 37.

(5) stabilization

The structures with a refractive index distribution obtained on a silicon substrate and a glass substrate as described above were heated at 150 ° C (the temperature at which component (A) does not decompose and component (A) and component (D) interact with each other) in for 2 minutes.

Then the entire surface of the structure again subjected to irradiation at 4.5 mW / cm ² using a Canon PLA-501F without a filter for 1 minute and heated in an oven at 200 ^C for 10 minutes to stabilize the structures with the refractive index distribution.

(7) re-irradiation and heating

The entire surface of the structures with a refractive index distribution stabilized as described above was re-irradiated at 4.5 mW / cm ² using a Canon PLA-501F without a filter for 1 minute and heated in an oven at 200 ° C for 10 minutes.

(8) stability assessment after repeated exposure and heating

The refractive indices of the low refractive index part and the high refractive index part of the re-irradiated and heated structure with the distribution of the refractive index obtained on the silicon substrate were measured in the same manner as described above in (3) for measuring the refractive index to assess the stability of the refractive index to re-exposure and heating.

The transparency of the low refractive index part and the high refractive index part of the re-irradiated and heated structure with the distribution of the refractive index obtained on the glass substrate was measured in the same manner as indicated in the transparency assessment in (4) in order to evaluate the stability of the transparency to re-irradiation and heat. The results are presented in table 5 and table 6.

Example 45

The estimates were carried out in the same manner as in Example 44, except that 50 parts by weight of the compound (A-12) were used as component (A), the temperature of the REV in step (2) (structure formation with a distribution of the refractive index) was changed as shown in table 5, and the heating temperature in stage (5) (stabilization) was changed as shown in table 6. The results are presented in table 5 and table 6.

Example 46

The evaluations were carried out in the same manner as in Example 44, except that 50 parts by weight of compound (A-15) were used as component (A), and the exposure value in step (2) (structure formation with distribution of refractive index) changed as shown in table 5. The results are presented in table 5 and table 6.

Example 47

Evaluation was carried out in the same manner as in Example 44, except that 50 parts by weight of compound (A-16) was used as component (A), 5 parts by weight

N- (2-nitrobenzyloxycarbonyl) pyrrolidine was used as component (C), the exposure level in step (2) (structure formation with a refractive index distribution) was changed as shown in table 5. The results are presented in table 5 and table 6.

Example 48

The evaluations were carried out in the same manner as in Example 44, except that a solution containing polymer (B-2) (equivalent to 50 parts by weight (solids content) of polymer (B-2)) was used as component (B ) The results are presented in table 5 and table 6.

Example 49

The evaluations were carried out in the same manner as in Example 44, except that 10 parts by weight of 1,4-bis (4,5-dihydro-2-oxazolyl) benzene was used as component (D) and the exposure value in step ( 2) (structure formation with a distribution of the refractive index) was changed, as shown in table 5. The results are presented in table 5 and table 6.

Example 50

The evaluations were carried out in the same manner as in Example 47, except that 10 parts by weight of 1,4-bis (4,5-dihydro-2-oxazolyl) benzene was used as component (D) and the exposure value in step ( 2) (structure formation with a distribution of the refractive index) was changed, as shown in table 5. The results are presented in table 5 and table 6.

Table 5 Example The conditions for the formation of the structure with the distribution of the indicator
refraction Optical properties before stabilization Refractive index Transparency Value
exposure (mJ / cm ² ) REV temperature (° C) Low Refractive Part High Refractive Part Part with a low refractive index (%) Part with a high refractive index (%) Example 44 fifty 130 1.44 1,53 99.3 99.0 Example 45 fifty 120 1.44 1.55 99.3 98.6 Example 46 20 130 1.44 1,52 99.3 99.0 Example 47 80 130 1.44 1,58 98.9 98.6 Example 48 fifty 130 1.44 1,52 99.3 99.1 Example 49 40 130 1.44 1,53 99.3 99.0 Example 50 90 130 1.44 1,58 98.9 98.6

Table 6 Example Stabilization conditions Optical properties after stabilization Indicator Transparency Temperature (° C) Low part
refraction High Performance Part
refraction Part with
low rate
refraction
(%) High Refractive Part
(%) Example 44 200 1.44 1,53 99.1 98.8 Example 45 140 1.44 1,54 99.1 98.5 Example 46 150 1.44 1,52 99.1 98.8 Example 47 150 1.44 1,57 98.7 98.4 Example 48 150 1.44 1,52 99.1 98.9 Example 49 150 1.44 1,53 99.1 98.8 Example 50 150 1.44 1,57 98.7 98.4

Example Optical properties after accelerated exposure Refractive index Transparency Low Refractive Part High Refractive Part Part with a low refractive index (%) Part with a high refractive index (%) Example 44 1.44 1,53 99.1 98.8 Example 45 1.44 1,54 99.1 98.5 Example 46 1.44 1,52 99.1 98.8 Example 47 1.44 1,57 98.7 98.4 Example 48 1.44 1,52 99.1 98.9 Example 49 1.44 1,53 99.1 98.8 Example 50 1.44 1,57 98.7 98.4

Example 51

50 parts by weight of compound (A-11) as component (A), a solution containing polymer (B-1), as component (B) (equivalent to 50 parts by weight (solids content) of polymer (B-1) ) and 1 part by weight of 4-phenylthiophenyl diphenylsulfonium trifluoromethanesulfonate as component (C) was dissolved in diethylene glycol ethyl methyl ether to a total solids content of 20%, and the resulting solution was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a solution compositions with a variable indicator pr refraction.

The formation of a coating film

The above solution was applied to a silicon substrate using a die and preliminarily fired on a hot plate at 100 ° C for 2 minutes to form a coating film with a thickness of 1.0 μm.

The formation of the structure with the distribution of the refractive index, stabilization, measurement of the refractive index and transparency assessment were carried out in the same manner as in example 37.

Changing porosity with a mercury porosimeter

The porosity of the low refractive index part and the high refractive index part of the above-obtained structure with a refractive index distribution was measured using a mercury porosimeter (Autopore 9200 from Shimadzu Corporation, minimum measured pore diameter of 34 E).

BJH pore distribution measurement

The pore distribution of the low refractive index part and the high refractive index part of the structure obtained above with the refractive index distribution was measured using the BJH method (from the first letters of the authors Barret, Joyner, Halenda, based on nitrogen gas absorption) using OMNISORP100 / 360 SERIES of COULTER Co., Ltd. The number of pores having a diameter of 100 nm or more is shown in Table 8.

Pore diameter measurement by observation under an electron microscope

The diameter of each pore in the part with a low refractive index and part with a high refractive index of the structure obtained above with a refractive index distribution was measured by observation under a transmission electron microscope to count pores having a diameter of 100 nm or more per 10 μm ² , with an arbitrary observation range.

Example 52

The estimates were carried out in the same manner as in Example 51, except that 50 parts by weight of the compound (A-12) were used as component (A), the temperature of the REV in step (2) (structure formation with a distribution of the refractive index) was changed as shown in table 7, and the type of component (D) and the stabilization temperature in step (5) (stabilization) were changed as shown in table 8. The results are presented in table 7 and table 8.

Example 53

The evaluations were carried out in the same manner as in Example 51, except that 50 parts by weight of compound (A-15) were used as component (A), and the exposure value in step (2) (structure formation with distribution of refractive index) changed as shown in table 7, and the type of component (D) and the stabilization temperature in step (5) (stabilization) were changed as shown in table 8. The results are presented in table 7 and table 8.

Example 54

The evaluations were performed in the same manner as in Example 51, except that 50 parts by weight of compound (A-16) was used as component (A), 5 parts by weight of N- (2-nitrobenzyloxycarbonyl) pyrrolidine was used as component (C), the exposure value in stage (2) (structure formation with a refractive index distribution) was changed as shown in table 7 and the type of component (D) in stage (5) (stabilization) was changed as shown in table 8. Results presented in table 7 and table 8.

Example 55

The evaluations were carried out in the same manner as in Example 51, except that the solution containing the polymer (B-3) (equivalent to 50 parts by weight (solids content) of the polymer (B-3)) was used as component (B ) The results are presented in table 7 and table 8.

Table 7 Example
The conditions for the formation of the structure with the distribution of the indicator
refraction Stabilization conditions Exposure value (mJ / cm ² ) Roar temperature
(° C) Component Type (D) Temperature (° C) Example 51 80 100 D-1 80 Example 52 80 100 D-2 20 Example 53 60 100 D-2 20 Example 54 100 100 D-1 80 Example 55 80 150 D-1 80

In table 7, the symbols for component (D) denote the following: D-1 - phenyl glycidyl ether (containing 10 mol.% Tetrabutylammonium bromide); D-2 - 1% aqueous solution of p-xylylenediamine.

Table 8 Example Refractive index Porosity Low Refractive Part High Refractive Part Part with a low refractive index (%) High part
refractive index (%) Example 31 1.31 1,54 28 0 Example 32 1.30 1.55 thirty 0 Example 33 1.27 1,54 38 0 Example 34 1.33 1,58 22 0 Example 35 1.37 1,54 eleven 0

Example Pore distribution Pore diameter Transparency Low Refractive Part High Refractive Part Low Refractive Part
(%) Part with a high refractive index (%) Example 31 0 0 98.5 98.1 Example 32 0 0 98.5 98.1 Example 33 0 0 98.5 98.2 Example 34 0 0 98.2 97.7 Example 35 0 0 98.5 98.0

Example 56 (obtaining optical fiber GI type (1))

50 parts by weight of compound (A-6) as component (A), 50 parts by weight of methyltrimethoxysilane condensate (weight average molecular weight 18000) as component (B), 1 part by weight of 4-phenylthiophenyl diphenyl sulfonium trifluoromethanesulfonate as component (C) and 1.5 parts by weight of 2- (2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl) -2H-benzotriazole as an ultraviolet light absorber was dissolved in methyl ethyl ketone to a total solids content of 70%. This solution was used as a fiber stock solution, was foamed and extruded from an injection nozzle having an outlet diameter of 1 mm at a speed of 1 m / min and the injected fiber was uniformly irradiated with light using a 250 mW ultrahigh-pressure mercury lamp (Ushio Inc. Spot Cure , i-beam illumination of 6.7 mW / cm ² ) from all sides using a ring light guide from Nippon PI Co., Ltd. (inner diameter 55 mm), and then heated at 200 ° C for 5 seconds on the emitting side of the infrared lamp 10 cm from it.

The acid formed from component (C), when irradiated from all sides, was mostly distributed near the surface of the fiber, and in addition, the decomposition of component (A) by heating gradually (gradient) decreased inward from the part located near the surface, thus giving GI type optical fiber, whose refractive index decreased in a parabolic manner from the central axis to the periphery. When the refractive index was measured using an interference refractometer, the maximum difference in the refractive index Δn between the center and the periphery was 0.09.

Example 57 (obtaining optical fiber GI type (2))

A GI type optical fiber was obtained in the same manner as in Example 56, except that 50 parts by weight of compound (A-5) was used as component (A). When the refractive index was measured using an interference refractometer, the maximum difference in the refractive index Δn between the center and the periphery was 0.11.

Example 58 (obtaining optical fiber GI type (3))

A GI type optical fiber was obtained in the same manner as in Example 56, except that 1 part by weight of 2- (4-methoxyphenyl) bis (4,6-trichloromethyl) -s-triazine was used as component (C) . When the refractive index was measured using an interference refractometer, the maximum difference in the refractive index Δn between the center and the periphery was 0.09.

Example 59 (obtaining GRIN lenses (1))

GRIN lenses, in which refractive indices were continuously distributed from the center to the periphery, were obtained by cutting thin disks from GI type optical fibers obtained in Examples 56-58.

Example 60 (obtaining GRIN lenses (2))

50 parts by weight of compound (A-2) as component (A), 50 parts by weight of methyltrimethoxysilane condensate (weight average molecular weight 18000) as component (B), 1 part by weight of trifluoromethanesulfonate

4-phenylthiophenyl diphenylsulfonium as component (C) and 1.5 parts by weight of 2- (2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl) -2H-benzotriazole as an ultraviolet light absorber were dissolved in methyl ethyl ketone to the total solids content of 70% and the resulting solution was molded into disk samples having a diameter of 2 cm and a thickness of 5 mm, under reduced pressure using a hot press. The diaphragm 2, which could open or close, was installed in a radiating device opposite the disk sample 1, as shown in Fig. 1, the disk sample was irradiated with ultraviolet radiation 4 having a wavelength of 365 nm, with an illumination of 30 mW / cm ² using a radiating device 3 by gradually opening the diaphragm 2, and the shutter speed was controlled so that the diaphragm 2 was fully open in 5 seconds, the irradiation was completed after 5 seconds and the disk sample was fired after irradiation at 120 ° C for 2 Inuit. In this way, an optically molded disk was obtained whose refractive index continuously increased from the center to the periphery. An optically molded product having a refractive index difference of 0.08 functioned as GRIN lenses with concave lens capabilities and demonstrated the potential for use as spectacle glasses for nearsightedness.

Example 61 (obtaining GRIN lenses (3))

A disk sample was obtained in the same manner as in Example 60. The upper and lower parts of the cylinder of the disk sample were protected from light, and light could only come from the side. In this state, the sample was irradiated with a 250 mW ultrahigh-pressure mercury lamp (Spot Cure from Ushio Inc., i-beam illumination 6.7 mW / cm ² ) using a ring light guide from Nippon PI Co., Ltd. (inner diameter 55 mm for 20 seconds, and calcined after irradiation at 120 ° C. for 2 minutes. An optically shaped disk was obtained whose refractive index continuously decreased from the center to the periphery. An optically shaped product having a difference in refractive index, component 0.08, functioned as GRIN lenses having convex lens capabilities.

Example 62 (obtaining a GI type optical waveguide)

50 parts by weight of compound (A-2) as component (A), 50 parts by weight of methyltrimethoxysilane condensate (weight average molecular weight 2000) as component (B) and 1 part by weight of 4-phenylthiophenyl diphenylsulfonium trifluoromethanesulfonate as component (C) dissolved in diethylene glycol ethyl methyl ether to a total solids content of 40%, and the resulting solution was filtered through a membrane filter having a pore diameter of 1.0 μm to obtain a solution containing a photosensitive composition with a variable I have a refractive index (S-1). 100 parts by weight of methyltrimethoxysilane condensate (weight average molecular weight 2000) used as component (B) and 1 part by weight SI-L150 (from Sanshin Kagaku Co., Ltd.) as a thermal acid generator was dissolved in diethylene glycol ethyl methyl ether to total a solids content of 40% to obtain a solution (S-2).

The solution (S-2) was initially applied to the surface of the silicon substrate using a centrifugal coating device and dried at 70 ° C for 10 minutes, and the entire surface of the formed coating film was exposed to ultraviolet radiation having an illuminance of 4.0 mW / cm ² and a wavelength of 365 nm, for 5 seconds to form a layer of the lower shell with a thickness of 10 μm. After that, a solution (S-1) was applied to the layer of the lower shell using a centrifugal coating device and dried at 70 ° C for 10 minutes to form an intermediate layer with a thickness of 10 μm, which was then exposed to ultraviolet radiation having an illumination of 4, 0 mW / cm ² and a wavelength of 365 nm, for 10 seconds through a photomask having an image of an optical waveguide and a width of 4 to 20 μm for 10 seconds. After that, the intermediate layer was fired after irradiation at 120 ° C for 2 minutes. The non-irradiated portion served as a central portion (core), and the irradiated portion served as a layer of the lateral sheath.

The solution (S-2) was applied to this intermediate layer using a centrifugal coating device and dried at 70 ° C for 10 minutes to obtain a layer of the upper shell 10 μm thick, the entire surface of which was then exposed to ultraviolet radiation having an illumination of 4 , 0 mW / cm ² and a wavelength of 365 nm, for 5 seconds and fired after irradiation at 120 ° C for 2 minutes, obtaining an optical waveguide.

The refractive indices of light having a wavelength of 1.550 nm for the formed upper, side, and lower shells were 1.42. In contrast, the refractive index of the center layer (core) for light with a wavelength of 1.550 nm was 1.50, and the maximum difference in refractive index Δn was 0.08. Since the obtained optical waveguide contained an optical acid generator in the upper and lower shells, diffusion occurred between the central layer and the upper shell and between the central layer and the lower shell. Thus, at the interfaces between the parts of the upper, lateral, and lower shells and the central layer, a refractive index distribution is created, and the resulting optical waveguide is a GI type waveguide. Concerning the obtained optical waveguide, in the case when the waveguide losses were obtained by measuring the amount of light emitted from the other end, while the light having a wavelength of 1300 nm entered from one end of the waveguide, they were 0.1 dB / cm or less .

Example 63 (obtaining an optical recording medium)

50 parts by weight of compound (A-2) as component (A), 50 parts by weight of methyltrimethoxysilane condensate (weight average molecular weight 2000) as component (B) and 1 part by weight of trifluoromethanesulfonate

4-phenylthiophenyl diphenylsulfonium as component (C) was dissolved in diethylene glycol ethyl methyl ether to a total solids content of 20%, and the resulting solution was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a solution containing a photosensitive composition with a variable indicator refraction. This solution was applied onto a flat polycarbonate substrate having a 60 nm thick aluminum reflective film deposited by sputtering using a centrifugal coating device and dried at 80 ° C for 2 minutes to form a layer with a variable refractive index of 1.0 μm thickness . After that, the variable refractive index layer was exposed to ultraviolet radiation having a wavelength of 365 nm and an illumination of 40 mW / cm ² through a photomask having a step width of 0.5 μm with a track width of 1.6 μm for 5 seconds and fired after irradiation at 12 ° C for 2 minutes. Thus, the difference in refractive index between the irradiated part and the non-irradiated part was 0.08 at 633 nm and could be excellently read as an optical recording medium.

Example 64 (obtaining an optical IC)

50 parts by weight of compound (A-2) as component (A), 50 parts by weight of methyltrimethoxysilane condensate (weight average molecular weight 2000) as component (B) and 1 part by weight of 4-phenylthiophenyl diphenylsulfonium trifluoromethanesulfonate as component (C) was dissolved in diethylene glycol ethyl methyl ether to a total solids content of 33%, and the resulting solution was filtered through a membrane filter having a pore diameter of 1.0 μm to obtain a solution containing a photosensitive composition with a varying the refractive index. This solution was applied to the surface of a glass substrate using a centrifugal coating device and dried at 70 ° C. for 10 minutes, and the applied layer was exposed to ultraviolet radiation having a wavelength of 365 nm and an illuminance of 4.0 mW / cm ² through a photomask having a width of 100 μm for 5 seconds and fired after irradiation at 120 ° C for 2 minutes. The result was an optical integrated circuit (IC) having a 100 micrometer structure with a refractive index distribution.

Example 65 (obtaining an optical diffraction grating)

The solution obtained in example 62 was used to obtain a film sample with dimensions of 2 cm × 1 cm × 10 μm. This sample was exposed to ultraviolet radiation having a wavelength of 365 nm and an illumination of 4.0 mW / cm ² . Parallel rays 9 from the irradiating device 8 were reflected by a reflector 7 placed at an angle of 45 °, and a film sample 5 was irradiated on the platform 6, as shown in FIG. 2. The sample was illuminated by an interference pattern formed by reflected light and direct emitted light. Upon irradiation, the sample was moved at a speed of 1 μm / min in the direction shown by the arrow in the figure, resulting in an optical diffraction grating having a 0.5 μm cycle.

Example 66 (obtaining a hologram)

Parallel rays having a wavelength of 365 nm and an illuminance of 4.0 mW / cm ² were divided into two optical paths using a half-mirror, one of them was allowed to pass through a transparent material (object) as signal light and it interfered with the other used as a reference light, and the resulting interference pattern was radiated onto the same optically molded product as in Example 65. The image of the material (object) recorded with high resolution was fixed by lighting of the obtained optically molded th light to reproduce the product.

Claims (17)

1. A radiation-sensitive composition with a variable refractive index, containing a compound (A) degradable by acid or base, a compound (B) not decomposable by acid or base, having a lower refractive index than said acid or base decomposable compound (A), sensitive to irradiation, a decomposing substance (C) generating an acid or base, and a solvent. 2. The composition according to claim 1, characterized in that the maximum difference between the refractive index of the part that is exposed to radiation and the refractive index of the part that is not exposed to radiation is 0.02 or more. 3. The composition according to claim 1 or 2, characterized in that the refractive index n _{B is} not degradable by acid or base of compound (B) and the refractive index n _{A of} decomposable acid or base of compound (A) satisfy the expression n _A -n _B ≥ 0, 05. 4. The composition according to any one of claims 1 to 3, characterized in that the non-degradable acid or base compound (B) is an acid-non-degradable polymer. 5. The composition according to claim 4, characterized in that the acid decomposable compound (A) contains at least one compound having at least one structure selected from the group consisting of structures represented by the following formulas (1) - (8) :

where R ¹ represents an alkylene group, an alkylene-arylene-alkylene group or an arylene group; R ² represents an alkylene group, an alkylene-arylene-alkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group;

where M represents Si or Ge; R ³ represents an alkylene group, an alkylene-arylene-alkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group; R ⁴ represents an oxygen atom, an alkylene group, an alkylene-arylene-alkylene group, an arylene group or a single bond; R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or a thioalkyl group; m is 0, 1 or 2;

where R ⁹ and R ¹⁰ each independently represents an alkylene group, an alkylene-arylene-alkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group; where R ¹¹ represents an oxyalkylene group or a single bond; R ¹² represents a hydrogen atom, an alkyl group, an alkylene-arylene-alkylene group or an aryl group;

where R ¹³ represents a hydrogen atom, an alkyl group or an aryl group;

where R ¹⁴ represents an alkylene group or structure represented by the following formulas (6) -1, (6) -2 or (6) -3:

where R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom, a chain alkyl group containing from 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 containing from 1 to 6 carbon atoms, an alkylthio group containing from 1 to 6 carbon atoms, a haloalkyl group containing from 1 to 6 carbon atoms, a haloalkoxy group containing from 1 to 6 carbon atoms, a haloalkyl group containing from 1 to 6 carbon atoms hydroxyalkyl a group containing from 1 to 6 carbon atoms, a mercaptoalkyl group containing from 1 to 6 carbon atoms, a hydroxyalkoxy group containing from 1 to 6 carbon atoms, a mercaptoalkylthio group containing from 1 to 6 carbon atoms, an aryl group containing from 6 to 10 carbon atoms, or an aralkyl group containing from 7 to 11 carbon atoms,

where R ¹⁹ represents an alkylene group;

where R ²⁰ represents an alkylene group;

where R ²¹ represents an alkylene group, an alkylene-arylene-alkylene group or an arylene group;

where R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a chain alkyl group containing from 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 containing from 1 to 6 carbon atoms, an alkylthio group containing from 1 to 6 carbon atoms, a haloalkyl group containing from 1 to 6 carbon atoms, a haloalkoxy group containing from 1 to 6 carbon atoms, a haloalkyl group containing from 1 to 6 carbon atoms hydroxyalkyl a group containing from 1 to 6 carbon atoms, a mercaptoalkyl group containing from 1 to 6 carbon atoms, a hydroxyalkoxy group containing from 1 to 6 carbon atoms, a mercaptoalkylthio group containing from 1 to 6 carbon atoms, an aryl group containing from 6 to 10 carbon atoms, or an aralkyl group containing from 7 to 11 carbon atoms. 6. The composition according to any one of claims 1 to 3, characterized in that the compound (B) which is not decomposable by acid or base is a polymer not decomposable by base. 7. The composition according to claim 6, characterized in that the base-decomposable compound (A) contains at least one compound having at least one structure selected from the group consisting of structures represented by the following formulas (9) - (12) :

where R ²⁶ represents an alkylene group, an aralkylene group or an arylene group; R ²⁷ represents an alkylene group, an aralkylene group, an arylene group, an alkylene-arylene-alkylene group, an alkylsilylene group or an alkylgermylene group; R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or a thioalkyl group; i and j are each independently 0 or 1;

where R ³² represents an alkylene group, an aralkylene group or an arylene group; R ³³ represents an alkylene group, an aralkylene group, an arylene group, an alkylene-arylene-alkylene group, an alkylsilylene group or an alkylgermylene group;

where R ³⁴ and R ³⁵ each independently represents an alkylene group, an aralkylene group, an arylene group, an alkylene-arylene-alkylene group, an alkylsilylene group or an alkyl germylene group;

where R ³⁶ and R ³⁷ each independently represents an alkylene group, an aralkylene group, an arylene group, an alkylene-arylene-alkylene group, an alkylsilylene group or an alkyl germylene group. 8. The composition according to any one of claims 1 to 7, characterized in that it further comprises a stabilizer (D), which is at least one substance selected from the group consisting of an amino compound, an epoxy compound, a tyrant compound, an oxetane compound, an alkoxymethylmelamine compound , alkoxymethylglucoluryl compound, alkoxymethylbenzoguanamine compound, alkoxymethylurea compound, isocyanate compound, cyanate compound, oxazoline compound, oxazine compound and silyl compound. 9. The composition according to claim 1, characterized in that it further comprises a stabilizer (D) and a catalyst for the interaction of the decomposable acid or base of compound (A) with a stabilizer (D). 10. The method of forming a structure with a distribution of the refractive index, consisting of regions with different refractive indices, in which a radiation-sensitive composition with a variable refractive index, containing compound (A) degradable by acid or base, compound (B) not decomposable by acid or base, is sensitive to radiation, the decomposing substance (C) generating an acid or base and the stabilizer (D) are irradiated and heated to react the stabilizer (D) with a degradable acid oh or base compound (A) of unexposed portion. 11. The method of forming a structure with a distribution of the refractive index, consisting of regions with different refractive indices, in which the composition with a variable refractive index containing decomposable acid or base compound (A), not decomposable acid or base compound (B), having a lower rate refractions than said acid or base decomposable compound (A) and radiation sensitive decomposing substance (C) generating acid or base are irradiated through a template of the structure and treated with a stabilizer (D) to react with the acid or base compound (A) of the non-irradiated portion that is decomposed with the stabilizer (D). 12. The method of forming a structure with a distribution of the refractive index, consisting of regions with different refractive indices, in which the composition with a variable refractive index containing decomposable acid or base compound (A), not decomposable acid or base compound (B), having a lower rate refractions than said acid or base decomposable compound (A) and radiation sensitive decomposing substance (C) generating acid or base are irradiated through the template structure and heated to decompose decomposable acid or base of the polymer is not exposed to the irradiation part. 13. The method according to claim 10, 11 or 12, characterized in that the formed structure with a distribution of the refractive index has pores or has no pores in the irradiated part. 14. The structure with the distribution of the refractive index formed by the method according to claim 10, 11, 12 or 13. 15. The structure according to 14, characterized in that it consists of a first region having or not having any pores, and a second region having a higher refractive index than the first region, and having no pores. 16. The structure of claim 15, wherein the first region has a lower modulus of elasticity than the second region. 17. An optical material having a structure with a distribution of the refractive index formed by the method according to claim 10, 11, 12 or 13.

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