JP2003222972A - Pattern forming material and image forming material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming material capable of pattern formation without carrying out a developing step after exposure and capable of forming definite two regions having a great difference between hydrophilicity and hydrophobicity by a polarity change and to provide an image forming material using the pattern forming material and capable of forming a high resolution image. <P>SOLUTION: The pattern forming material has on a support a pattern forming layer comprising a high molecular compound having a functional group whose hydrophilicity or hydrophobicity is varied by light and having a structure which can directly be bonded to the top of the support by a chemical bond, wherein the pattern forming layer is irradiated with light of ≤700 nm to vary the hydrophilicity or hydrophobicity of the surface of the pattern forming layer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming material and an image forming material, and more particularly to a pattern forming material capable of easily forming an image having excellent resolution, and an image forming useful as a display material using the same. Regarding materials.

[0002]

2. Description of the Related Art Conventionally, as a pattern forming method,
A method of obtaining a pattern by photolithography, which is often used for photoresists, is mainly used. In this method, after light irradiation and pattern formation,
A hydrophilic / hydrophobic pattern is formed through a complicated process of developing. The method that requires a developing solution in the developing process is not suitable for the environment, and a simple pattern forming method that does not require the developing process has been desired.

As a means for solving these problems, recently, surface patterning using a pattern forming material which does not require development has been proposed. Examples of the material used for the surface patterning include “Surface” Vol. 33, No. 6 (1995), 374
-379, the photodegradable 1,2,3,4-tetrahydronaphthylideneimino-p-styrenesulfonate. The method is a sulfone that is hydrophobic under light irradiation by using 1,2,3,4-tetrahydronaphthylideneimino-p-styrene sulfonate and a copolymer of methacrylic acid ester or styrene. A functional group is substituted with a hydrophilic sulfonic acid from an acid ester to form a hydrophilic / hydrophobic pattern in exposed and unexposed areas without going through a development process.

However, such a surface patterning method has a problem that the hydrophilic portion generated by light irradiation is melted out, and it is difficult to obtain the essential hydrophilic / hydrophobic pattern. In order to solve this problem, it is also possible to synthesize a copolymer having a crosslinkable group introduced, and to take a means to crosslink the polymer to improve the film strength.
Although the strength of the hydrophilic part is improved, the hydrophilic functional group penetrates into the crosslinkable polymer chain, the hydrophilic part becomes insufficient in hydrophilicity, the difference between hydrophilicity and hydrophobicity becomes small, and a pattern with high resolution is formed. It turns out that a new problem arises that it is difficult to obtain.

Kunihiro Ichimura "Polymer Pr"
eprints "Vol. 49, No. 12 (200
0) discloses a method utilizing a photodimerization reaction using a compound having a bispyridinioethylene structure. This is because by adsorbing a compound having a bispyridinioethylene structure on a glass substrate, the bispyridinioethylene structure is dimerized by light irradiation to form a hydrophobic part, which is exposed only by exposing it to saline solution. The part and the unexposed part form a hydrophilic / hydrophobic pattern. However, even with this method, the difference between hydrophilicity and hydrophobicity was not sufficient.

Further, as a method for forming a dense pattern with controlled orientation, for example, Japanese Patent Laid-Open No. 2000-2477 is used.
Japanese Patent Laid-Open No. 99 proposes a method for producing a functional organic molecular thin film. According to this method, a fine pattern can be formed, but the imagewise writing is performed by UV exposure through a mask such as a lith film as in the conventional image forming method of a lithographic printing plate precursor. Therefore, there is a problem that the process is complicated.

Attention has been drawn to various methods of directly writing imagewise on pattern forming materials from digitized image data without using media such as a lith film, and various proposals have been made. If such a digitized writing method is used, it is expected that a clear image will be formed regardless of the area and characteristics of the pattern forming material. Based on the data, for example, by performing light irradiation, there is no need to perform other steps such as development, and a pattern forming technique that provides sufficient hydrophilicity and hydrophobicity has not yet been established. is there.

[0008]

The object of the present invention, which has been made in consideration of the above-mentioned drawbacks of the prior art, is that a pattern can be formed after the exposure without performing a developing step, and the hydrophilicity can be obtained by changing the polarity. It is an object of the present invention to provide a pattern forming material capable of forming two distinct regions having a large difference in hydrophobicity and an image forming material capable of forming a high resolution image using the pattern forming material.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by applying a polymer compound whose surface characteristics are changed by exposure, and complete the present invention. Came to.

That is, the pattern forming material of the present invention is
A pattern forming layer comprising a polymer having a functional group whose hydrophilicity / hydrophobicity is changed by light and having a structure capable of being directly bonded to the support by a chemical bond is provided on the support. Further, it is characterized in that the hydrophilicity / hydrophobicity of the surface of the pattern forming layer is changed by performing light irradiation of 700 nm or less. Here, a structure having a functional group (hereinafter, appropriately referred to as a polar conversion group) whose hydrophilicity / hydrophobicity is changed by light used for the pattern forming layer and having a structure capable of being directly bonded to the support by a chemical bond is used. The polymer compound has a linear polymer compound bound to the surface of the support by a direct chemical bond at the end of the polymer chain, or via a trunk polymer compound at the end of the polymer chain. In a preferred embodiment, the linear polymer compound is bound to the surface of the support by a chemical bond. The polar conversion group used in the pattern forming material of the present invention, the hydrophilicity / hydrophobicity is changed by light with high sensitivity, and the polarity conversion group is characterized by the excellent mobility of the formed hydrophilicity / hydrophobicity on the surface. Since it appears, there is a large difference between hydrophilicity and hydrophobicity, and two distinct regions can be formed.

Further, the image-forming material of the present invention has a functional group on the support, the hydrophilicity / hydrophobicity of which is changed by light, and
An image recording layer composed of a polymer compound having a structure capable of being directly bonded by a chemical bond is provided on the support, and the image recording layer is irradiated with light of 700 nm or less to change the hydrophilicity / hydrophobicity of the surface of the image recording layer. It is characterized in that organic or inorganic molecules capable of forming a visible image are adsorbed to the region where the hydrophilicity / hydrophobicity is changed. Thus, the image forming material of the present invention,
Depending on the polarity of the surface of the polymer compound having a functional group whose hydrophilicity and hydrophobicity is changed by light, organic or inorganic molecules that form a visible image are selectively formed in hydrophilic and hydrophobic regions according to the polarity of the surface. Since image formation is performed by adsorption, a high-resolution image based on digital data can be obtained regardless of the area of the image forming material.

The polymer compound having a polar conversion group which is used as the image recording layer of the image forming material is bound to the support directly at its terminal or through the trunk polymer compound, and further, a visible pattern is formed. Since the organic or inorganic molecules to be formed are ionically strongly adsorbed on the surface of the recording layer depending on the polarity, both the image area and the non-image area exhibit high strength and abrasion resistance. As a result, high-intensity image formation is possible even with a thin layer.
When a dye is used as an organic molecule or various pigments are used as an inorganic molecule, it is considered to be capable of forming an image with excellent sharpness even in a thin layer because it is ionically adsorbed to a polar conversion group. To be Furthermore, in the present invention,
The polarity conversion group, which has the ability to adsorb organic or inorganic molecules, has a graft chain structure with high mobility, so the adsorption rate is extremely fast compared to the adsorption of molecules by general cross-linked polymer membranes, and per unit area The feature is that the amount of molecules that can be adsorbed on is increased. In the image-forming material of the present invention, it is possible to make the image-recording layer thinner and further improve the sensitivity while maintaining the image quality, and the polymer compound constituting the image-recording layer is used as the support ( Since it is directly chemically bonded to the image receiving material), it has an advantage that it is excellent in durability even if it is a thin layer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The pattern forming material and image forming material of the present invention will be described in detail below. The end of the polymer chain having a functional group whose hydrophilicity and hydrophobicity is changed by light, which is a feature of the pattern forming material and the image forming material of the present invention, is chemically bonded to the surface of the support directly or through the trunk polymer. Means for forming the pattern forming layer and the image recording layer will be described.

[Surface Graft Polymerization] The pattern forming layer and the image recording layer according to the present invention are prepared by a means generally called surface graft polymerization. Graft polymerization is a method of synthesizing a graft (grafting) polymer by giving an active species on the chain of a polymer compound, thereby further polymerizing another monomer that initiates the polymerization, and a polymer giving an active species in particular. When a compound forms a solid surface it is called surface graft polymerization.

As the surface graft polymerization method for realizing the present invention, any known method described in the literature can be used. For example, New Polymer Experiments 10, edited by Japan Society of Polymer Science, 1994, published by Kyoritsu Shuppan Co., Ltd., P135 describes a photograft polymerization method and a plasma irradiation graft polymerization method as a surface graft polymerization method. Further, the radiation irradiation graft polymerization method using γ-rays, electron beams and the like is described in Adsorption Technology Handbook, NTS Corporation, supervised by Takeuchi, published in 1999.2, p203, p695. As a specific method of the photograft polymerization method, there is disclosed in JP-A-10-296895.
The methods described in JP-A No. 11-119413 and JP-A No. 11-119413 can be used.

In addition to these means, a trialkoxysilyl group, an isocyanate group, an amino group may be added to the end of the polymer compound chain to form a surface graft layer in which the end of the polymer compound chain is chemically bonded directly. It can also be formed by providing a reactive functional group such as a group, a hydroxyl group, or a carboxyl group and coupling the functional group present on the surface of the support with the functional group. Incidentally, the support surface in the present invention, the surface, the end of the polymer compound having a polar conversion group has a function of chemically bonding directly or through the stem polymer compound, The support itself may have such surface characteristics, or an intermediate layer may be separately provided on the support and the intermediate layer may have such characteristics.

Further, as a means for preparing a surface in which the end of the polymer compound chain having a polar conversion group is chemically bound via the trunk polymer compound, a coupling reaction with a functional group on the surface of the support is carried out. Functional group is added to the side chain of the backbone polymer, and a graft polymer compound incorporating a polymer compound chain having a functional group whose hydrophilicity / hydrophobicity changes as a graft chain is synthesized. It can also be formed by a coupling reaction with a group.

[Functional group whose hydrophilicity / hydrophobicity changes] Next, a functional group (polarity conversion group) whose hydrophilicity / hydrophobicity changes with light, which is one of the features of the pattern forming material and image forming material of the present invention, will be described. . The polarity conversion group used in the present invention is not sensitive to long-wavelength exposure such as infrared rays and heat, but directly decomposed by light irradiation of a predetermined wavelength, and undergoes ring-opening or dimerization reaction, resulting in high sensitivity and polarity. It is characterized by changing. There are two types of polarity conversion groups, a functional group that changes from hydrophobic to hydrophilic and a functional group that changes from hydrophilic to hydrophobic.

(Functional group changing from hydrophobicity to hydrophilicity) As the functional group changing from hydrophobicity to hydrophilicity, for example, functional groups represented by the following general formulas (1) to (9) are used. it can.

In the present invention, examples of the functional group which changes from hydrophobic to hydrophilic include those represented by the following general formula (1).

[0021]

[Chemical 1]

(In the general formula (1), L represents an organic group composed of a polyvalent non-metal atom necessary for connecting to the polymer skeleton. R ¹ and R ² are each independently an alkyl group or an aromatic group. Represents a group ring group, and R ¹ and R ² may combine with each other to form a ring.)

R ¹ and R ^{2 in} the general formula (1) each independently represent an alkyl group or an aromatic ring group, and R ¹ and R ²
May combine with each other to form a ring. The alkyl group represented by R ¹ and R ² preferably has 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group,
Octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, cyclohexyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group,
A cyclopentyl group and the like, and R ¹ and R ² are
- (CH _{2) n} -, may be bonded to each other in units of (n = 1~4). Among these, R ¹ and R ² are-
It is particularly preferable that the units of (CH ₂ ) _n − and (n = 1 to 4) are bonded to each other to form a ring.

The alkyl group represented by R ¹ and R ² is
It may be substituted or unsubstituted, and as the introduced substituent, a monovalent non-metal atomic group excluding hydrogen is used. Preferred examples include halogen atoms such as F, Br, Cl and I, a hydroxyl group, an alkoxy group, an amino group,
Formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chlorophenyl group Methylphenyl group,
Examples thereof include a hydroxyphenyl group, a methoxyphenyl group, an ethoxyphenyl group, a phenoxyphenyl group and an acetoxyphenyl group.

The aromatic ring group represented by R ¹ and R ² preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a naphthyl group and a mesityl group. , Phenyl group and naphthyl group are preferred.
Further, the aromatic ring group represented by R ¹ and R ² may be substituted or unsubstituted, and as the introduced substituent, a monovalent non-metal atomic group except hydrogen is used. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl group, alkoxy group, amino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group and aryloxycarbonyl group.

More specific examples of R ¹ and R ² are those in which the terminal structure including the carbonyl group to be bonded and the nitrogen atom bonded to the carbonyl group is represented by the following formula. preferable.

[0027]

[Chemical 2]

Further, the polyvalent linking group consisting of a non-metal atom represented by L in the general formula (1) means 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 It is composed of 1 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. Of these, a substituted or unsubstituted divalent benzene ring group or an alkyl group having 1 to 8 carbon atoms is preferable. Examples of more specific linking groups include those formed by combining the following structural units.

[0029]

[Chemical 3]

When the polyvalent linking group has a substituent, the substituent may be an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, or a carbon number 6 to 16 such as a phenyl group or a naphthyl group. Up to aryl groups, hydroxyl groups, carboxyl groups, sulfonamide groups, N-sulfonylamide groups, acetoxy groups such as acyloxy groups having 1 to 6 carbon atoms, methoxy groups, ethoxy groups having 1 to 6 carbon atoms An alkoxy group, a halogen atom such as chlorine or bromine,
It is possible to use an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a cyclohexyloxycarbonyl group, a cyano group, and a carbonic acid ester group such as t-butyl carbonate.

In the present invention, examples of the functional group that changes from hydrophobic to hydrophilic include those represented by the following general formula (2).

[0032]

[Chemical 4]

(In the general formula (2), L represents an organic group composed of a polyvalent non-metal atom necessary for connecting to the polymer skeleton. R ³ and R ⁴ are each independently a monovalent substituent. Represents a group, and R ³ and R ⁴ may combine with each other to form a ring)

R ³ and R ^{4 in} the general formula (2) each independently represent a monovalent substituent, specifically, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, a formyl group, an acyl group. Represents a group, a carboxyl group, a cyano group, or an aromatic ring group. When R ³ and R ⁴ are alkyl groups, it is preferably in the range of 1 to 8 carbon atoms, for example,
Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group ,
Examples thereof include an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclopentyl group, and R.
¹ and R ² may be bonded to each other in a unit of — (CH ₂ ) _n —, (n = 1 to 4). Among these,
R ^3, R ⁴ is a methyl _{group, - (CH 2) n -} , (n = 1~
It is particularly preferred that it is a cyano group or a ring structure in which units 4) are bonded to each other.

Further, an alkyl group represented by R ³ and R ⁴ , a hydroxyl group, an alkoxy group, an amino group, a formyl group,
The acyl group, the carboxyl group, or the cyano group may be substituted or unsubstituted, and as the substituent to be introduced, a monovalent nonmetallic atomic group except hydrogen is used. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl group, alkoxy group, amino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, phenyl group, Biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, etc. Is mentioned.

The aromatic ring group represented by R ³ and R ⁴ preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a naphthyl group and a mesityl group. , Phenyl group and naphthyl group are preferred.
The aromatic ring group represented by R ³ and R ⁴ may be substituted or unsubstituted, and as the introduced substituent, a monovalent non-metal atomic group except hydrogen is used. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl group, alkoxy group, amino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group and aryloxycarbonyl group. Above all, R
^More preferably, ³ and R ⁴ are an aromatic ring group having at least one nitro group and having 6 to 14 carbon atoms, which may be substituted or unsubstituted.

As more specific examples of the above R ³ and R ⁴ , those in which the terminal structure including (-N = C) in the general formula (2) is represented by the following formula are particularly preferable.

[0038]

[Chemical 5]

The polyvalent linking group consisting of a non-metal atom represented by L in the general formula (2) has the same meaning as L in the general formula (1), and the preferred examples are also the same. Further, a more specific linking group is the same as the one formed by combining the structural units represented by the general formula (1). When the polyvalent linking group has a substituent, the substituent is the same as that used in the general formula (1).

In the present invention, examples of the functional group which changes from hydrophobic to hydrophilic include those represented by the following general formula (3).

[0041]

[Chemical 6]

(In the general formula (3), L represents an organic group consisting of a polyvalent non-metal atom necessary for connecting to the polymer skeleton. R ⁵ and R ⁶ are each independently an alkyl group or an aromatic group. Represents a group ring group.)

R ⁵ and R ^{6 in} the general formula (1) each independently represent an alkyl group or an aromatic ring group. Also,
R ^5, R ⁶ represents an organic group comprising polyvalent non-metallic atoms necessary for coupling to the polymer backbone. The alkyl group represented by R ⁵ and R ⁶ is, for example, a linear alkyl group having 1 to 25 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or isopropyl group. Base, t
It is preferably a branched alkyl group having 1 to 8 carbon atoms such as -butyl group, s-butyl group, isopentyl group, neopentyl group. Of these, a methyl group, an ethyl group, an isopropyl group, and a t-butyl group are preferable. Further, the alkyl groups represented by R ⁵ and R ⁶ may be substituted or unsubstituted, and as the introduced substituent, a monovalent non-metal atomic group excluding hydrogen is used. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl group, alkoxy group, amino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, phenyl group,
Biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, etc. Is mentioned.

The aromatic ring group represented by R ⁵ and R ⁶ is
It includes a carbocyclic aromatic ring group and a heterocyclic aromatic ring group. The carbocyclic aromatic ring group preferably has 6 to 19 carbon atoms, and among them, a benzene ring such as a phenyl group, a naphthyl group, an acetracenyl group, a pyrenyl group, a biphenyl group, a xylyl group and a mesityl group. Are more preferably 1 to 4 rings. As the heterocyclic aromatic ring group, those having 3 to 20 carbon atoms and 1 to 5 hetero atoms are preferable, and among them, a pyridyl group, a furyl group, a quinolyl group in which a benzene ring is condensed, and a benzofuryl group. More preferred are groups, thioxanthone groups and carbazole groups. Further, the aromatic ring group represented by R ⁵ and R ⁶ may be substituted or unsubstituted, and as the introduced substituent, a monovalent non-metal atomic group except hydrogen is used. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl group, alkoxy group, amino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group and aryloxycarbonyl group.

The polyvalent linking group consisting of a non-metal atom represented by L in the general formula (3) has the same meaning as L in the general formula (1), and the preferred examples are also the same. Further, a more specific linking group is the same as the one formed by combining the structural units represented by the general formula (1). When the polyvalent linking group has a substituent, the substituent is the same as that used in the general formula (1).

In the present invention, examples of the functional group which changes from hydrophobic to hydrophilic include those represented by the following general formula (4).

[0047]

[Chemical 7]

(In the general formula (4), L represents an organic group composed of a polyvalent non-metal atom necessary for connecting to the polymer skeleton. R ⁷ represents an alkyl group or an aromatic ring group.)

R ^{7 in the} general formula (4) represents an alkyl group or an aromatic ring group. The alkyl group represented by R ⁷ preferably has 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group,
Examples thereof include an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group. The alkyl group represented by R ⁷ may be substituted or unsubstituted, and as the introduced substituent, a monovalent non-metal atomic group except hydrogen is used. Preferred examples are F and B
halogen atom such as r, Cl, I, hydroxyl group, alkoxy group, amino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, phenyl group, biphenyl group,
Examples include naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group and acetoxyphenyl group. .

The aromatic ring group represented by R ⁷ preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a naphthyl group and a mesityl group. A naphthyl group is preferred. Further, the aromatic ring group represented by R ⁷ may be substituted or unsubstituted, and as the introduced substituent, a monovalent non-metal atomic group except hydrogen is used. Preferred examples include halogen atoms such as F, Br, Cl and I, hydroxyl group, alkoxy group, amino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group and aryloxycarbonyl group.

As a more specific example of the above R ⁷ , a structure represented by the following formula is particularly preferable.

[0052]

[Chemical 8]

The polyvalent linking group consisting of a non-metal atom represented by L in the general formula (4) has the same meaning as L in the general formula (1), and the preferred examples are also the same. Further, a more specific linking group is the same as the one formed by combining the structural units represented by the general formula (1). When the polyvalent linking group has a substituent, the substituent is the same as that used in the general formula (1).

In the present invention, examples of the functional group which changes from hydrophobic to hydrophilic include those represented by the following general formulas (5) and (6).

[0055]

[Chemical 9]

(In the general formulas (5) and (6), L represents an organic group composed of a polyvalent non-metal atom necessary for connecting to the polymer skeleton.)

Further, the above general formulas (5) and (6)
The polyvalent linking group consisting of a non-metal atom represented by L has the same meaning as L in the general formula (1), and the preferred examples are also the same. Further, a more specific linking group is the same as the one formed by combining the structural units represented by the general formula (1). When the polyvalent linking group has a substituent, the substituent is the same as that used in the general formula (1).

Further, in the present invention, as the functional group which changes from hydrophobicity to hydrophilicity, there may be mentioned known functional groups represented by the following general formulas (7) to (9). . In addition, L in these formulas is also synonymous with L in the said General formula (1).

[0059]

[Chemical 10]

The general formula (7) is based on P. Jaganna
tan, SPIE (1994), p. 2195, a quinonediazide polymer. The general formula (8) is based on M. L. Schilling, Macro
mol (1995), page 110. In formula (6), R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 5 carbon atoms. ) The general formula (9) is based on M. Tsunooka, J. Po
lym. Sci. Chem. Ed, (1996), 2
The oxime ester group-containing polymer described on page 181.

(Functional Group Changing from Hydrophilicity to Hydrophobicity) In the present invention, the functional group changing from hydrophilicity to hydrophobicity includes those represented by the following general formula (I).

—L—N═N—SO ₃ M General Formula (I) (In the general formula (I), L represents an organic group composed of a polyvalent non-metal atom necessary for linking to the polymer skeleton. M is NH
⁴⁺ or represents a monovalent cation containing a metal atom. )

The polyvalent linking group consisting of a non-metal atom represented by L in the general formula (I) has the same meaning as L in the general formula (1) in the functional group changing from hydrophobic to hydrophilic. The same applies to the preferred examples. Further, a more specific linking group is the same as the one formed by combining the structural units represented by the general formula (1). When the polyvalent linking group has a substituent, the substituent is the same as that used in the general formula (1).

The metal atom contained in M of the general formula (I) is an alkali metal atom, Al, Cu or Z.
n, in addition to polyvalent metal atoms such as alkaline earth metals. When the metal atom contained in M is a monovalent metal atom, for example, sodium (Na), M is —SO ₃ ^{— at} the end of the functional group represented by the general formula (I).
And the general formula (I) is -L-N = N-S
It becomes O ₃ Na. In addition, when the metal atom contained in M is a polyvalent metal atom, the polyvalent metal forms a monovalent cation together with the ligand, and at the terminal of the functional group represented by the general formula (I). Combines with SO ₃ ⁻ . It is also possible to adopt a structure in which a polyvalent metal atom serves as a polyvalent cation and is bonded to the terminal —SO ₃ ^— of the functional groups represented by the general formula (I).

In the present invention, another example of the functional group which changes from hydrophilic to hydrophobic is a bispyridinioethylene group.

[Support Surface] The pattern-forming material and image-forming material of the present invention are a surface graft layer in which the terminal of the above-mentioned polymer compound having a polar conversion group is chemically bonded directly or through a trunk polymer compound. And a terminal of the polymer compound has a support surface on which the end can be chemically bonded directly or through the trunk polymer compound. As described above, the surface of the support itself may have such characteristics, and an intermediate layer having such characteristics may be provided on the surface of the support.

(Support Surface or Intermediate Layer) Such a support surface may be either an inorganic layer or an organic layer as long as it has characteristics suitable for providing the surface graft layer by graft synthesis. . Further, in the present invention, since the pattern-forming layer made of a thin polymer compound and the image-forming material exhibit a change in hydrophilicity / hydrophobicity, the polarity of the surface does not matter, and hydrophilicity or hydrophobicity is not a problem. Good.

Such an intermediate layer is a layer having an organic surface, particularly when the thin layer polymer of the present invention is synthesized by a photograft polymerization method, a plasma irradiation graft polymerization method, or a radiation irradiation graft polymerization method. A layer of an organic polymer is preferable. Further, as the organic polymer, epoxy resin, acrylic resin, urethane resin, phenol resin, styrene resin, vinyl resin, polyester resin, polyamide resin, melamine resin, formalin resin and other synthetic resins, gelatin, casein, cellulose, Although any of natural resins such as starch can be used, a photograft polymerization method,
In the plasma irradiation graft polymerization method, the radiation irradiation graft polymerization method, etc., the initiation of graft polymerization proceeds from the extraction of hydrogen from the organic polymer, so polymers that are susceptible to hydrogen abstraction, especially acrylic resins, urethane resins, styrene resins, vinyl resins It is particularly preferable to use a polyester resin, a polyamide resin, an epoxy resin or the like from the viewpoint of production suitability. Such an intermediate layer may also serve as a substrate (support) described later, or may be an intermediate layer provided on the support, if necessary.

Further, in the pattern forming material and the image forming material of the present invention, the polymer compound is directly added from the viewpoint of the formability of the pattern forming layer and the image recording layer and the adhesiveness to the pattern forming layer and the image recording layer. As the chemically bonded support, a support having a roughened surface can also be used. When a roughened support is used, its surface properties preferably satisfy the following conditions. As a preferred state of the roughened support, the center line average roughness (Ra) of the two-dimensional roughness parameter is 0.1 to 0.1.
1 μm, maximum height (Ry) is 1 to 10 μm, ten-point average roughness (Rz) is 1 to 10 μm, average interval of irregularities (Sm) is 5 to 80 μm, average interval of local peaks (S) is 5 to 80 μm.
m, maximum height (Rt) is 1 to 10 μm, center line peak height (Rp) is 1 to 10 μm, center line valley depth (Rv) is 1
The range is 10 μm, and one satisfying one or more of these conditions is preferable, and it is more preferable that all of them are satisfied.

(Support Substrate) The support (substrate) used in the pattern forming material and image forming material of the present invention and having a support surface having the above-mentioned characteristics on the surface thereof is a dimensionally stable plate-like material. It is preferable that, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, trisulfate). Cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic film laminated or vapor-deposited with the above metals. That. As the support used in the present invention, a polyester film or an aluminum plate is preferable, and among them, a polyester film which can also serve as the lower layer is particularly preferable. The aluminum plate used as the base material may be subjected to known surface treatments such as the above-described roughening treatment and anodizing treatment, if necessary.

In the case of using a plastic film such as a polyester film which is another preferred embodiment, the one subjected to the above-mentioned roughening treatment is used for the purpose of improving the formability of the hydrophilic surface and the adhesion. be able to.

When the support used in the pattern forming material and the image forming material of the present invention also serves as the intermediate layer, the film itself made of the resin material described in detail for the intermediate layer can be used. In this case, it is preferable that the surface of the support to which the polymer compounds forming the pattern forming layer and the image recording layer are directly chemically bonded is roughened as described above.

[Pattern Forming Method] The pattern forming (writing) on the pattern forming material of the present invention has a wavelength of 700 n.
It is performed by irradiation with light of m or less. As a means of light irradiation, as long as it is possible to cause polarity conversion in the pattern forming layer, that is, by decomposing, ring-opening or dimerizing the above-mentioned polarity converting group, it is possible to change the hydrophilicity / hydrophobicity. , Either can be used. For example, light irradiation with an ultraviolet lamp, visible light, or the like is possible. Examples of these light sources include mercury lamps, metal halide lamps, xenon lamps, chemical lamps and carbon arc lamps. Others, electron beam, X-ray, ion beam, Deep-
UV light and high-density energy beam (laser beam) can also be used.

Further, in order to perform direct writing by digital data of a computer, a method of causing polarity conversion by laser exposure is preferable. As the laser, carbon dioxide laser, nitrogen laser, Ar laser, He /
Gas laser such as Ne laser, He / Cd laser, Kr laser, liquid (dye) laser, ruby laser, Nd / YA
Solid state laser such as G laser, GaAs / GaAlAs, I
Semiconductor laser such as nGaAs laser, KrF laser, X
An eCl laser, a XeF laser, an excimer laser such as Ar ₂ or the like can be used.

[Image Forming Method] As described above, when light irradiation is performed, hydrophilic and hydrophobic regions are formed according to the polarity of the polarity conversion group. For example, when a pattern forming layer (image forming layer) that changes polarity from hydrophobic to hydrophilic is used, a hydrophilic pattern (hydrophilic region) is formed by hydrophilic graft in the exposed region, and a hydrophobic functional group is formed in the unexposed region. The surface of the polymer-containing layer having a group serves as a hydrophobic region. A visible image is formed by attaching organic or inorganic molecules capable of forming a visible image to the hydrophilic / hydrophobic pattern. Next, an image forming method of the image forming material according to the present invention will be described.

In the image forming mechanism of the image forming material of the present invention, the polarity converting group of the polymer compound in the image recording layer is polarity converted in the light irradiation region to have a negative charge. By adsorbing organic or inorganic molecules to this area, the area becomes the image area and the area where the organic or inorganic molecules are not adsorbed becomes the non-image area.

Further, a hydrophilic substance such as a water-soluble dye is adsorbed to the hydrophilic region obtained by converting the polarity, or a hydrophobic substance such as a lipophilic dye is adsorbed to the hydrophobic region. Images can also be formed.

(Organic or Inorganic Molecule) Here, the organic or inorganic molecule to be adsorbed on the polarity-converted surface may be a low molecular compound or a high molecular compound as long as it is a substance capable of forming a visible image. Good. The term "capable of forming a visible image" refers to a substance having absorption in the visible wavelength region, and specific examples thereof include colored dyes or pigments, various light-impermeable pigments, and metal fine particles. To be

(Relationship between Polarity of Surface Graft Polymerization and Organic or Inorganic Molecules) An image recording having a functional group which changes from hydrophobic to hydrophilic as represented by the general formula (1) concretely exemplified above. In the layer, only the exposed areas become selectively negatively charged, and a visible image is formed by adsorbing a positively charged molecule, for example, a cationic dye. When such an image forming mechanism is used, only the exposed portion is converted in polarity to have a molecular adsorption ability, so that not only a single color image but also a multicolor image can be formed. That is, the image forming material is exposed to light so that a cationic dye having a yellow color tone is adsorbed in the exposed area and the excess dye is removed by washing with water to form a yellow image. At this time, since the polarity conversion group in the unexposed portion is not affected, the same image forming material is exposed again in an imagewise manner to cause polarity conversion, and the cation having a magenta color tone in the exposed region. It is possible to form a multicolor image by stepwise imagewise exposure such as forming a magenta image by adsorbing a dye and then forming a cyan image in the same manner.

Examples of the cationic organic or inorganic molecule that can be used for image formation include a cationic dye, a cationically charged inorganic pigment, metal fine particles, and a coated pigment formed by forming a cationic surface layer on the surface. , Coated metal fine particles and the like. Here, as the cationic dye that can be used, a known dye can be appropriately selected and used according to the purpose such as color tone and image density. Such a cationic dye is electrically attracted to the surface of the image recording layer due to the function of the acidic group (sulfonic acid group, carboxylic acid group, etc.) as the polarity conversion group, and penetrates not only to the surface but also to the inside to finally It is considered that an image is formed by bonding with an acidic group on. Because this image is due to ionic interactions,
Strongly adsorbs and forms a high-density image with high fastness with less dye.

As the cationic dye, a dye having an alkylamino or aralkylamino bond at the terminal of the chromophore, a dye having an acid amide bond such as a sulfonic acid alkylamide bond, an azo dye having a group capable of forming a cation, or a methine dye. And heterocyclic compounds such as thiazole and azo dyes. Examples of the skeleton of the cationic dye include triphenylmethane, diphenylmethane, xanthene, acridine, azine, thiazine, thiazole, oxazine, azo, and the like. Examples of such a dye include “New Dye Chemistry”, Yutaka Hosoda, Gihodo, ( 316 of 1957)
See pages 322 to 322.

As another image forming mechanism, for example, in an image recording layer having a cation graft polarity conversion functional group such as an ammonium group described in JP-A-10-296895, the surface of the original recording layer material is positively charged. Therefore, only the exposed region loses the electric charge. When a molecule having a negative charge, such as an acid dye, is adsorbed on the surface, the acid dye is adsorbed on the unexposed portion to form a visible image. When using such an image forming mechanism,
Since organic or inorganic molecules are adsorbed only on the unexposed portion, an image forming material suitable for monochromatic image formation can be obtained.

Examples of the anionic organic or inorganic molecule that can be used for such image formation include acidic dyes, anionically charged inorganic pigments, metal fine particles, and coated pigments formed by forming an anionic surface layer on the surface. , Coated metal fine particles and the like. Here, as the acid dye that can be used,
Known dyes can be appropriately selected and used according to purposes such as color tone and image density. Examples of such an acid dye include dyes such as azo type, anthraquinone type, triphenylmethane type, xanthene type, azine, and phosphorous, and any of these can be used.
Specifically, for example, C.I. I. Acid Yellow
1, C.I. I. Acid Orange 33, C.I. I.
Acid Red 80, C.I. I. Acid Viol
et 7, C.I. I. Acid Blue 93 and the like, and such dyes are described, for example, in "Handbook of Dyes" edited by the Society of Organic Synthetic Chemistry, Maruzen, (1970) pp. 392-4.
Details are given on page 71.

When using charged fine particles,
The central part of the fine particles called the core may be either an inorganic substance or an organic substance, and when the core is an inorganic substance, preferably gold,
Precious metal particles such as silver, palladium, rhodium and platinum. When the core is an organic substance, it is preferably an organic polymer. The particle size of the charged fine particles is preferably in the range of 0.1 nm to 1000 nm, more preferably in the range of 1 nm to 100 nm. If the particle size is smaller than 0.1 nm, the handling property is poor, and if it is larger than 1000 nm, the contact area for ionically bonding with the polarity-converted functional group is small and the strength of the formed image tends to be deteriorated. There is. In particular, when a transparent support such as glass or a transparent plastic film is used, it is preferably 0.2 to 100 nm, more preferably 1 to 10 nm, from the viewpoint of ensuring light transmission and visibility. Use one.

The fine particles having high density and electric charge on the surface can be obtained by the method of Toru Yonezawa et al. Yonezawa
a, Chemistry Letters. , (199
9) page 1061, T.I. Yonezawa, Lan
gumuir (2000), vol16, 5218 and Toru Yonezawa, Polymer preprints, Ja.
pan vol. It can be created by the method described in 49.2911 (2000). Yonezawa et al. Have shown that the metal-sulfur bond can be used to chemically modify the surface of metal particles at high density with charged functional groups.

The organic or inorganic molecule is not limited to one kind,
Multiple types can be used in combination as necessary. Further, in order to obtain a desired color tone, a plurality of materials may be mixed in advance. As a method of adsorbing an organic or inorganic molecule to a portion whose polarity has been changed, a liquid in which a charged organic or inorganic molecule is dissolved or dispersed on the surface is applied to a support surface image-wise changed in polarity by exposure or the like. And a method of immersing the surface of the image-polarized support in these solutions or dispersions. In both cases of coating and dipping, an excessive amount of organic or inorganic molecule is supplied, and since introduction by a sufficient ionic bond between the polar conversion group is made, the solution or dispersion and the surface of the support are The contact time is preferably about 10 seconds to 60 minutes, more preferably about 1 minute to 20 minutes.
It is preferable that the organic or inorganic molecule is bonded in the maximum amount that can be adsorbed to the polarity-converted region of the support surface in terms of the sharpness, color tone and durability of the image. From the viewpoint of adsorption efficiency, the concentration of the solution or dispersion should be at least 10-20.
About wt% is preferable.

The amount of these organic or inorganic molecules to be used can be appropriately selected depending on the image forming mechanism of the image forming material. However, since they are introduced by ionic adsorption and are introduced in a state close to a monomolecular film, Compared with the amount of color-forming materials and colored materials used for general image-forming materials, a small amount,
An image with high density and high sharpness can be formed. Further, when a light-impermeable material such as an inorganic pigment or a metal pigment is adsorbed by using the resin film having the above-mentioned surface texture on the support, or a light-transmitting colored dye is adsorbed. In this case, a light-transmissive pattern forming material such as OHP or street lighting, and a display material can be easily obtained.

The image-forming material of the present invention on which an image is formed by the above method is expected to have a wide variety of uses as various pattern-forming materials or display materials.

[0089]

[Example 1]

(Pattern forming material: Preparation of image forming material) Thickness 0.1
A 88 mm corona-treated polyethylene terephthalate film (product name: M4100, manufactured by Toyobo Co., Ltd.) was used as a support, and the following photopolymerizable composition was coated on the surface using a rod bar No. 18 and then at 80 ° C. for 2 minutes. It was dried to form an intermediate layer having a film thickness of 6 μm. Then, the support on which the intermediate layer is formed is replaced with a 400 W high pressure mercury lamp (model number: UVL-
400P, manufactured by Riko Kagaku Sangyo Co., Ltd.) was used for irradiation for 10 minutes for pre-curing.

[0090] (Interlayer coating liquid) ・ Allyl methacrylate / methacrylic acid copolymer   (Copolymerization molar ratio 80/20, average molecular weight 100,000) 2 g ・ Ethylene oxide modified bisphenol A diacrylate   (IR125 Wako Pure Chemicals) 4g ・ 1-Hydroxycyclohexyl phenyl ketone 1.6 g ・ 1-Methoxy-2-propanol 16 g

The pre-cured support was placed on acrylic acid (1
0 wt%) and sodium periodate (NaIO ₄ ,
It was immersed in an aqueous solution containing 0.01 wt%), and was irradiated with light for 30 minutes under an argon atmosphere using the above 400 W high-pressure mercury lamp. After the light irradiation, the obtained film was thoroughly washed with ion-exchanged water to obtain a support grafted with acrylic acid.

Next, 1 liter of water and N-ethyl-N '
An aqueous solution consisting of 40 g of (3-dimethylaminopropyl) carbodiimide hydrochloride and 6 g of N-hydroxysuccinimide was prepared, and the support on which acrylic acid was grafted was immersed therein for 1 hour to perform ester conversion. After that, 6 g of 2-nitrobenzylphenol was further added,
The reaction was carried out to obtain a pattern forming material A in which a polymer having a photodegradable functional group was fixed on the surface.

(Pattern formation: image formation) The obtained pattern forming material A was imagewise exposed with a laser (beam diameter 20 μm) which emits blue light having a wavelength of 400 nm. After exposure,
Pattern forming material A is methylene blue (Wako Pure Chemical Industries)
After immersion in a 0.1% by weight aqueous solution for 10 minutes and washing with distilled water, methylene blue selectively adhered imagewise to the laser-exposed portion, and a clear blue image was formed.

[Example 2] (Pattern forming material: preparation of image forming material) 500 ml
12 g of N-hydroxyphthalimide in a three-necked flask
And 8.7 g of pyridine and 140 g of acetonitrile,
And p-styrenesulfonyl chloride (20 g) dissolved in acetonitrile (40 g) were added under a nitrogen stream at room temperature.
Stir for 5 hours. Then, the solution was put into 1 liter of water, and the precipitated solid was collected by filtration and washed with water to obtain the following exemplified monomer (1).

[0095]

[Chemical 11]

In a 500 ml three-necked flask, 50 g of the exemplified monomer (1), 3.4 g of mercaptopropyltrimethoxysilane and 220 g of dimethylacetamide.
, And under a nitrogen stream at 65 ° C., 0.5 g of 2,2-azobis (2,4-dimethylvaleronitrile) was added,
After stirring at the same temperature for 6 hours, the mixture was cooled to room temperature. Thereafter, the solution was put into 2 liters of ethyl acetate, and the precipitated solid was collected by filtration and washed with water to obtain the following exemplified monomer (2).

[0097]

[Chemical 12]

The obtained Exemplified Monomer (2) was dissolved in propylene glycol monomethyl ether acetate / methyl ethyl ketone = 4/1 to prepare a 10 mass% solution. Into this solution, slide glass (2
(5 mm × 75 mm × 5 mm) was immersed for 10 minutes, then taken out, washed with acetonitrile, and dried at 110 ° C. for 10 minutes to obtain a pattern forming material B having a polymer having a photodegradable group fixed on the surface.

(Pattern formation: image formation) The obtained pattern forming material B was imagewise exposed with a laser (beam diameter 20 μm) which emits blue light having a wavelength of 400 nm. After exposure,
Pattern forming material B is methylene blue (manufactured by Wako Pure Chemical Industries)
After immersion in a 0.1% by weight aqueous solution for 10 minutes and washing with distilled water, methylene blue selectively adhered imagewise to the laser-exposed portion, and a clear blue image was formed.

Example 3 (Pattern Forming Material: Preparation of Image Forming Material) The following reactions were carried out while darkening the room or wrapping the flask with aluminum foil while protecting it from light. First, 24 g of sodium sulfite and 40 g of sodium carbonate are dissolved in 250 ml of water to prepare a solution. Next, 15.02 g of p-aminoacetanilide was added to 100 ml of water and 36.8 ml of concentrated HCl (3
2%) and cooled to 0-5 ° C using a cooling bath,
Prepare the solution. Then, 6.8 g of sodium nitrite is diluted in 15 ml of water to prepare a solution. The solution is added dropwise to the solution with cooling (<5 ° C.), then it is stirred for 10 minutes. After filtration, the mixed solution is rapidly poured into the solution under vigorous stirring. Then, the mixed solution is stirred for 30 minutes. The mixed solution may be red at the start of stirring, but turns yellow after a few minutes. Then, the solid product in the solution is filtered off from the solution.

The solid product formed is dissolved in 150 ml of water, 8 g of NaOH are added, then the solution is heated to 50 ° C. for 1 hour and subsequently cooled to 0 ° C. Then, with cooling, 19.66 ml of concentrated HCl (32%) is added to the solution. Then 100 ml of 1% picric acid (pier)
inic acid) and about 33.6 in about 350 ml of water
and a solution of g sodium carbonate dissolved therein are further poured into the solution. Then, the temperature of the solution before adding methacrylic acid chloride is adjusted to less than 5 ° C. Then, 15 ml of methacrylic acid chloride is added very slowly to the solution from the dropping funnel (where the solution foams very much). The resulting mixture is stirred at 0-5 ° C for 1 hour and then at room temperature for 1 hour. Then add 300 ml of saturated sodium acetate solution and cool the solution in the refrigerator (about 4 ° C).
Save it all night. The solid product formed is filtered and
Dry for 17 hours under reduced pressure at ° C. For the removal of the inorganic salts, 150 ml of the product are dissolved in N, N-dimethylformaldehyde (DMF), stirred at room temperature for at least 2 hours and filtered. Then, for the purpose of precipitation, the filtrate was poured into 2 liters of diethyl ether, then filtered, and dried under vacuum for 3 days to obtain the following exemplified monomer (3).

[0102]

[Chemical 13]

In a 500 ml three-necked flask, 50 g of the exemplified monomer (3), 3.4 g of mercaptopropyltrimethoxysilane and 220 g of dimethylacetamide.
, And under a nitrogen stream at 65 ° C., 0.5 g of 2,2-azobis (2,4-dimethylvaleronitrile) was added,
After stirring at the same temperature for 6 hours, the mixture was cooled to room temperature. Then, the solution was put into 2 liters of ethyl acetate, and the precipitated solid was collected by filtration and washed with water to obtain the following exemplified monomer (4).

[0104]

[Chemical 14]

The exemplary monomer (4) obtained was dissolved in propylene glycol monomethyl ether acetate / methyl ethyl ketone = 4/1 to prepare a 10% by mass solution. Into this solution, slide glass (2
(5 mm × 75 mm × 5 mm) was soaked for 10 minutes, then taken out, washed with acetonitrile and dried at 110 ° C. for 10 minutes to obtain a pattern forming material C having a polymer having a photodegradable group fixed on the surface.

(Pattern formation: image formation) The obtained pattern forming material C was imagewise exposed by a laser (beam diameter 20 μm) which emits blue light having a wavelength of 400 nm. After exposure,
Pattern forming material C is methylene blue (manufactured by Wako Pure Chemical Industries)
After immersion in a 0.1% by weight aqueous solution for 10 minutes and washing with distilled water, methylene blue selectively adhered image-wise to the unexposed portion of the laser to form a clear blue image.

[0107]

EFFECTS OF THE INVENTION According to the present invention, it is possible to form a pattern after the exposure without performing a developing process, and to form two distinct regions having a large difference in hydrophilicity and hydrophobicity due to a change in polarity. It is possible to provide a pattern forming material capable of performing the above, and an image forming material capable of forming a high resolution image using the pattern forming material. Therefore, the pattern forming material and the image forming material of the present invention are expected to have a wide range of applications in the future.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA17 AB14 AB20 AC01 AC08                       AD01 BH03 FA37                 2H096 AA28 AA30 BA20 CA05 EA04                       HA09                 2H123 AE00 AE01 BA00 BA01 CA00                       CA22 FA00

Claims (3)

[Claims] 1. A pattern forming layer comprising a polymer compound having a functional group whose hydrophilicity / hydrophobicity is changed by light and having a structure capable of being directly bonded to the support by a chemical bond. A pattern forming material, wherein the pattern forming layer is irradiated with light of 700 nm or less to change the hydrophilicity / hydrophobicity of the surface of the pattern forming layer. 2. A polymer compound having a functional group whose hydrophilicity / hydrophobicity is changed by light and having a structure capable of being bonded to the support by a direct chemical bond is a direct chemical bond at the end of the polymer chain. A linear polymer compound bound to the surface of the support by means of, or a linear polymer bound to the surface of the support by a chemical bond at the end of the polymer chain via a trunk polymer compound. The pattern forming material according to claim 1, wherein the pattern forming material is a polymer compound. 3. An image recording layer comprising a polymer compound having a functional group whose hydrophilicity / hydrophobicity is changed by light on a support and having a structure capable of being directly bonded to the support by a chemical bond. By irradiating the image recording layer with light having a wavelength of 700 nm or less, the hydrophilicity / hydrophobicity of the surface of the image recording layer is changed, and an organic or inorganic molecule capable of forming a visible image is adsorbed in a region where the hydrophilicity / hydrophobicity is changed. Characteristic image forming material.