JP2005314712A - Composition for forming metal particulate and metal particulate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition with which metal particulate (particularly, metal nanoparticle) can be easily and efficiently formed at high reducibility. <P>SOLUTION: The composition is composed of: a polysilane compound; and a metal compound (e.g., a noble metal compound) capable of forming the metal particulate by reduction. The polysilane compound may be a copolymer of polysilane and a vinyl monomer comprising a unit having affinity for the metal compound and/or metal particulate. The ratio of the metal compound may be, e.g., about 1 to 40 pts.wt. to 100 pts.wt. of the polysilane compound. By allowing active energy rays to act on the composition, the polysilane compound is decomposed, thus the metal particulate (particularly, nanoparticle) can be formed. The method can be applied to various methods, and, e.g., it is also possible that the composition is applied to a substrate, so as to be exposed to form metal particulate, and further, development is performed, thus a metal particulate-containing pattern is formed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a composition for producing fine metal particles (particularly metal nanoparticles) useful in optical applications (such as optical waveguides) and biotechnology, metal fine particles obtained using the composition, and a method for producing the same.

  Metal nanoparticles (metal fine particles), unlike metal atoms and bulk metals, exhibit unique electronic and optical properties such as quantum size effects and nonlinear optical properties [Solid Physics, Vol. 24, No. 10 (non-patent Reference 1)]. Therefore, application of these metal nanoparticles having unique phenomena to single-electron transistors, nonlinear optical elements, optical waveguides and the like in the fields of optical communication, optoelectronics, optical information processing, and the like are being considered [ Adv. Matter. Vol. 13, No. 19, page 1501 (Non-Patent Document 2)]. In addition, metal nanoparticles induce phenomena such as surface enhanced Raman scattering. For this reason, gold nanoparticles adsorbed on affinity ligands such as antibodies, enzymes, and protein A are attracting attention as sensors in the bio field (such as immunoassays) [Surface, Vol. 34, No. 2]. 32 (Non-Patent Document 3)]. Furthermore, the use of metal nanoparticles as a coloring material exhibiting good color development over a long period of time has been studied [Industrial Materials, Vol. 52, No. 4, Page 1 (Non-Patent Document 4)].

Until now, metal nanoparticles have been synthesized as colloidal solutions by reducing metal salts in solution in the presence of a compound having a functional group (protecting group) for stabilizing the particles. For example, gold nanoparticles can be obtained by reducing a chloroauric (III) acid (HAuCl ₄ ) solution to which a thiol compound is added using a reducing agent such as sodium borohydride [Surface, Vol. 34]. 7, page 56 (Non-Patent Document 5)]. Platinum nanoparticles can be prepared by irradiating a platinum chloride (IV) acid solution in the presence of a long-chain alkylammonium chloride with a high-pressure mercury lamp having an output of 100 W for 24 hours [Polymer Papers, Vol. 57 No. 6, page 363 (Non-Patent Document 6)]. Silver nanoparticles can be obtained by reducing silver perchlorate with sodium borohydride in the presence of sodium polyphosphate [J. Am. Chem. Soc. 112, 4657 (Non-Patent Document 7)]. Furthermore, rhodium nanoparticles can be obtained by adding sodium hydroxide to an aqueous solution containing rhodium chloride and polyvinyl alcohol to change it to rhodium hydroxide, followed by hydrogen reduction [J. Colloid Science, Vol. 3, page 363 (Non-patent Document 8)].

  On the other hand, in order to apply metal nanoparticles to various devices, it is necessary to mix and disperse metal nanoparticles, a binder resin, and a solvent to form a coating solution, and then form a thin film by a coating method such as spin coating. . For example, in JP-A-5-224006 (Patent Document 1), in the presence of a polymer having a pyrrolidone group (such as polyvinylpyrrolidone), sodium borohydride or the like is added as a reducing agent to reduce the metal salt. The obtained stabilized ultrafine metal particles are further dispersed in a general-purpose polymer (such as acrylonitrile-styrene copolymer) that stabilizes the particles. In addition, a metal nanoparticle composition in which rhodium nanoparticles are dispersed in polyvinyl alcohol has also been reported [Surface, Vol. 17, page 279 (Non-patent Document 9)].

  However, with these methods, the reducing agent does not have sufficient reducing performance, and it is difficult to efficiently generate metal nanoparticles with high reducing properties. Moreover, in preparation of a metal nanoparticle, it is necessary to add each component (a metal salt, a reducing agent, a compound which has a functional group (protecting group) etc.) in steps, and a preparation process is complicated. Therefore, in the above method, a sufficient amount of metal nanoparticles cannot be efficiently obtained in a short time, and it is not practical, so industrial production is difficult. Furthermore, the metal nanoparticles (or coating liquid containing metal nanoparticles) obtained by these methods may cause aggregation or the like when used or stored for a long period of time, and the stability or storage stability is not sufficient. . In addition, metal nanoparticles (or thin films containing metal nanoparticles) obtained by these methods often have insufficient adhesion to a substrate (such as an inorganic substrate) and are difficult to pattern.

  Furthermore, in order to apply metal nanoparticles to various devices, it is often necessary to form a pattern in order to exhibit functions. In order to form a pattern, after forming a nanoparticle-containing thin film using a non-photosensitive resin as a binder, a method using a lithography process in which a resist is additionally formed, and a photosensitive resin in which the binder resin itself is made photosensitive. There are two methods of directly developing a nanoparticle-containing thin film using

However, in the former method, first, a step of blending metal nanoparticles, a resin, and a solvent is required, and further complicated steps of resist application, exposure, development, etching, and resist stripping are required. In the latter method, a lithography process is not necessary, but a compounding process is necessary, and a resin must be selected in consideration of compatibility with nanoparticles, stability, and photosensitivity. It is not practical because of its poor nature.
JP-A-5-224006 (Claims and Examples) "Solid Physics, Vol. 24, No. 10" “Adv. Matter. Vol. 13, No. 19, p. 1501” "Surface, Vol. 34, No. 2, p. 32" "Industrial Materials, Vol. 52, No. 4, Page 1" "Surface, Vol. 34, No. 7, p. 56" "Polymer Papers, Vol.57, No.6, p.363" "J. Am. Chem. Soc. 112, 4657" “J. Colloid Science, Vol. 3, p. 363” “Surface, Vol. 17, p. 279”

  Accordingly, an object of the present invention is to provide a composition (or coating solution) capable of easily and efficiently producing metal fine particles (particularly metal nanoparticles), metal fine particles obtained from the composition, and production of the metal fine particles. It is to provide a method.

  Another object of the present invention is a composition that can remarkably suppress or prevent agglomeration of metal fine particles even when used (or stored) for a long period of time, and can generate metal fine particles having excellent stability (or storage stability). An object (or a coating film thereof), metal fine particles obtained from the composition, and a method for producing the metal fine particles.

  Still another object of the present invention is to provide a composition (or a coating film thereof) capable of patterning and forming a pattern containing metal fine particles easily and efficiently with a high pattern forming property without requiring a separate resist, and this It is providing the pattern (negative pattern) obtained using a composition (or coating film).

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that when an active energy ray is applied to a composition (or a coating film thereof) containing a polysilane compound and a metal compound (such as a metal salt), the polysilane compound Decomposes and acts as a reducing agent for the metal compound to produce metal fine particles (particularly metal nanoparticles) easily and efficiently with high reducibility, and the metal fine particles produced by this method can be produced over a long period of time. It is found that the coating film is excellent in long-term stability without causing agglomeration, and that the coating film can be easily formed into a pattern corresponding to an exposure pattern with a high pattern forming property. completed.

  That is, the composition of the present invention is a composition for producing metal fine particles (particularly metal nanoparticles), and is composed of a polysilane compound and a metal compound capable of producing the metal fine particles by reduction. The polysilane compound may be composed of polysilane (or polysilane unit), and may be, for example, a copolymer of polysilane and a vinyl monomer containing a unit having affinity for a metal compound. Such a vinyl monomer has, for example, at least one group selected from an amide group, an amino group, a nitrogen ring group, an acyl group, an alkoxy group, an ether group, a carboxyl group, a thio group, and a sulfonic acid group. It may be a monomer.

  The said metal compound may be comprised with periodic table 8-11 group metal (for example, noble metal). Specific metal compounds include, for example, chlorinated noble metal acids (such as chloroauric acid). The ratio of the metal compound may be, for example, about 1 to 400 parts by weight with respect to 100 parts by weight of the polysilane compound. The composition can also be used as a coating composition (coating liquid). The coating composition may be composed of a polysilane compound, a metal compound, and a solvent. Therefore, the present invention includes a coating film obtained by applying the composition (or coating composition) on a substrate.

  The metal fine particles can be usually produced (or prepared) by decomposing a polysilane compound by applying an active energy ray to the composition. The active energy ray may be at least one selected from actinic rays (particularly ultraviolet rays) and heat rays. Such a method for producing fine metal particles can be applied to various uses. For example, the composition may be applied to a substrate (for example, an inorganic substrate such as a glass substrate), exposed to generate metal fine particles, and further developed to form a pattern containing the metal fine particles.

  The present invention includes metal fine particles (particularly nanoparticles) obtained by the production method, and also a pattern obtained by the pattern formation method.

  In the present specification, “metal fine particles” include not only metal fine particles generated by reduction of metal compounds but also components (such as decomposition products of polysilane compounds) present on or near the surfaces of metal fine particles. The term “metal fine particle component” (or metal colloid) is used.

  Since the composition of the present invention is composed of a polysilane compound capable of generating radicals having high reducibility by decomposition, metal fine particles (particularly metal nanoparticles) can be produced easily and efficiently. In addition, the composition of the present invention remarkably suppresses the aggregation of metal fine particles even if it is used (or stored) for a long time because the decomposition product of the polysilane compound protects and stabilizes the surface of the metal fine particles. Alternatively, metal fine particles having excellent stability (or storage stability) can be generated. Therefore, in the present invention, metal fine particles can be produced practically and industrially advantageously. Furthermore, in the present invention, a pattern containing metal fine particles can be patterned and formed easily and efficiently with a high pattern forming property without requiring a separate resist.

  The composition of the present invention (hereinafter sometimes referred to as a polysilane composition) is composed of a polysilane compound and a metal compound capable of generating the metal fine particles by reduction. That is, in the composition of the present invention, as described later, the metal compound can be reduced by a decomposition product (radical) of the polysilane compound to generate metal fine particles (or metal fine particle components).

[Polysilane compound]
The polysilane compound only needs to be composed of at least polysilane (or polysilane unit or polysilane unit), for example, (a) a compound composed only of polysilane units (that is, polysilane), and (b) polysilane. And a polysilane compound composed of a unit bonded to the polysilane and having affinity for the metal compound and / or metal fine particles.

(Polysilane)
The polysilane (unit) constituting the polysilane compound is not particularly limited as long as it is various polysilanes having a Si—Si bond, such as linear, branched, cyclic, and network (hereinafter sometimes simply referred to as polysilane). . Usually, polysilane is often composed of at least one unit among the structural units represented by the following formulas (1) to (3).

(In the formula, R ^{1 to} R ³ are the same or different and are a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkenyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkenyl group, an aryl group, an aryloxy group. , An aralkyl group, an aralkyloxy group, or a silyl group, and m, n, and p are positive integers)
In the formulas (1) to (3), _{examples of the} alkyl group include C _1-14 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl and pentyl groups (preferably C _1-10 alkyl groups, more preferably C _1-6 alkyl groups). Examples of the alkoxy group include C _1-14 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, pentyloxy groups (preferably C _1-10 alkoxy groups, more preferably C _1-6 alkoxy groups). ). Examples of the alkenyl group include C _2-14 alkenyl groups such as vinyl and allyl groups (preferably C _2-10 alkenyl groups, more preferably C _2-6 alkenyl groups). Examples of the cycloalkyl group include C _5-14 cycloalkyl groups such as cyclopentyl and cyclohexyl groups (preferably C _5-10 cycloalkyl groups, more preferably C _5-8 cycloalkyl groups). _{Examples of the} cycloalkyloxy group include C _5-14 cycloalkyloxy groups such as a cyclohexyloxy group (preferably a C _5-10 cycloalkyloxy group, more preferably a C _5-8 cycloalkyloxy group). Examples of the cycloalkenyl group include C _5-14 cycloalkenyl groups such as a cyclopentenyl group and a cyclohexenyl group (preferably a C _5-10 cycloalkenyl group, more preferably a C _5-8 cycloalkenyl group). Examples of the aryl group include C _6-20 aryl groups such as phenyl and naphthyl groups (preferably C _6-15 aryl groups, more preferably C _6-12 aryl groups). Examples of the aryloxy group include C _6-20 aryloxy groups such as phenoxy and naphthyloxy groups (preferably C _6-15 aryloxy groups, more preferably C _6-12 aryloxy groups). Examples of the aralkyl group include C _6-20 aryl-C _1-4 alkyl groups such as benzyl and phenethyl groups (preferably C _6-10 aryl-C _1-2 alkyl groups). Examples of the aralkyloxy group include C _6-20 aryl-C _1-4 alkyloxy groups (preferably C _6-10 aryl-C _1-2 alkyloxy groups) such as benzyloxy and phenethyloxy groups. Examples of the silyl group include Si _1-10 silyl groups (preferably Si _1-6 silyl groups) such as a silyl group, a disilanyl group, and a trisilanyl group.

These substituents (groups R ¹ , R ² or R ³ ) are further substituted with substituents [eg, halogen atoms (chlorine atoms, fluorine atoms, etc.), alkyl groups (eg, C _1-4 alkyl such as methyl groups, etc.). Group, etc.), an alkoxy group (for example, C _1-4 alkoxy group such as methoxy group), an aryl group (phenyl group, naphthyl group, etc.) and the like].

Among these substituents (groups R ¹ , R ² or R ³ ), preferred substituents include a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxy group, and a silyl group. included.

In the formula (1), the combination of R ¹ and R ² may be a combination of aryl groups (such as a phenyl group), and a preferable combination is, for example, (a1) a C _1-4 alkyl group. (Especially methyl groups), (a2) combinations of _C1-4 alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) can be exemplified, and in particular, at least one of R ¹ and R ² is an aryl group A combination that is (particularly a phenyl group) (for example, the combination of the above (a2)) is preferable. Preferred R ³ is a C _1-4 alkyl group (particularly a C _1-2 alkyl group such as a methyl group) or an aryl group (particularly a phenyl group).

The types of R ¹ , R ^2, and R ³ may be different depending on the number of repeating structural units (number of m, n, p).

  Specific examples of the polysilane (unit) include (i) a linear or cyclic polysilane represented by the formula (1), and (ii) a branched polysilane (polysilin) represented by the formula (2). Or a branched polysilane represented by the formula (3), (iii) a combination of structural units represented by the formulas (1) to (3) (for example, the formula (1) and the formula (2) A combination of the formula (1) and the formula (3), a combination of the formula (1), the formula (2), and the formula (3)), and the like. Polysilanes may be used alone or in combination of two or more.

  In the polysilane having the structural unit, the values of m, n, and p may be, for example, about 2 to 10,000, preferably about 3 to 1,000, and more preferably about 3 to 500 (for example, 3 to 100). . In the cyclic polysilane represented by the formula (1), the value of m may be about 12 or less (for example, about 3 to 12, preferably about 4 to 12, and more preferably about 5 to 10). Moreover, in the polysilane which has a structural unit represented by the said Formula (2) or (3), n or p can be suitably selected from the said range (especially 2-100, Preferably about 2-50). Furthermore, the value of m + n + p is, for example, about 2 to 10,000, preferably about 3 to 1000 (for example, 5 to 1000), and more preferably about 5 to 500 (for example, 5 to 100). The polysilane may be a copolymer.

The terminal group of the structural unit represented by the formulas (1) to (3) may be composed of the substituent R ¹ , R ² or R ³ , and may be a halogen atom (chlorine atom, bromine atom, iodine atom, etc.) Or a silyl group substituted with the substituent R ¹ , R ^2, R ³ or the like.

A preferred polysilane is a linear or cyclic polysilane (for example, polymethylphenylsilane) in which at least one of the substituents R ¹ and R ² is an aryl group (particularly a phenyl group) in the formula (1). In the linear polysilane (unit), the terminal group may be composed of the inactive group (such as trimethylsilyl group or triphenylsilyl group).

  In addition, as polysilane, what is described in Unexamined-Japanese-Patent No. 4-218561 etc. by which the chemical structure and the manufacturing method are disclosed, for example may be used, and a commercial item may be used.

(Polysilane compound (b))
As described above, the polysilane compound (b) including the unit having affinity is bonded to the polysilane (polysilane unit), the metal compound (or metal atom constituting the metal compound) and / or metal fine particles. Specifically, the unit is composed of units having affinity for metal fine particles generated by reduction of the metal compound (hereinafter sometimes referred to as affinity units).

  When a polysilane compound having such an affinity unit (or polymer unit) is used, the production efficiency and stability of metal fine particles can be improved. Specifically, in the composition, when the polysilane compound has an affinity for the metal compound, the polysilane compound can be efficiently brought close to the metal compound, and a decomposition product of the polysilane compound with respect to the metal compound. The reduction effect (reduction efficiency) can be further improved, and nanometer (nm) size metal fine particles can be efficiently generated. Further, when the polysilane compound has an affinity for the metal fine particles, the affinity unit (and the decomposition product of the polysilane) are immediately present in the vicinity of the metal fine particles generated by photoreduction, and the metal fine particles are It may be stabilized (or protected) (that is, free metal fine particles do not exist), or the aggregation of metal fine particles can be effectively suppressed, and long-term storage stability is further improved. Furthermore, it is expected that the polysilane decomposition product will also coat the outer side of the metal fine particles, which is considered to be one of the factors that increase the storage stability. The polysilane compound (b) only needs to have an affinity for at least one of the metal compound and the metal fine particles, but usually has at least an affinity for the metal fine particles.

The affinity unit can be composed of an affinity group (or complex salt-forming group) for a metal compound (or a metal atom constituting the metal compound) or a metal fine particle (or metal atom). Examples of such affinity groups include nitrogen atom-containing groups [amino groups, substituted amino groups (such as dialkylamino groups), amino groups such as imino groups (—NH—), amide groups (—CON <), cyano groups, and the like. Group, nitro group, nitrogen ring group (5- to 8-membered nitrogen ring group such as pyridyl group, carbazole group and the like), oxygen atom-containing group [ether group, hydroxyl group, carboxyl group, alkoxy group (for example, methoxy group, C _1-6 alkoxy groups such as ethoxy group, propoxy group, butoxy group, preferably C _1-4 alkoxy group, especially C _1-2 alkoxy group), formyl group, ketone group (—CO—), ester group (— COO-), oxygen ring groups (such as 5- to 8-membered oxygen ring groups such as tetrahydropyranyl group)], sulfur atom-containing groups [thio group (-S-), mercapto group, alkylthio group (methylthio group) Such as C _1-4 alkylthio group such as an ethylthio group), a sulfo group, a halogen atom (a chlorine atom, a bromine atom) can be exemplified. The affinity group may form a salt (such as an alkali metal salt such as a sodium salt). The affinity unit may contain these affinity groups alone or in combination of two or more. The affinity unit only needs to be composed of an affinity group, and may be an affinity group or a group containing an affinity group.

The affinity unit may be bonded (or introduced) to polysilane as described above. Specific examples of the polysilane compound (b) include, for example, a copolymer (polysilane copolymer) of (b1) polysilane [or its constituent monomer (such as a silane compound)] and a vinyl monomer containing the affinity unit. ), (B2) The affinity unit (or the group containing the affinity unit) is directly or via a side chain (the group R ¹ , R ² , R ^3, etc.) on the silicon atom constituting the polysilane. Examples include bonded polysilane. A preferred polysilane compound (b) is a polysilane copolymer (b1) from the viewpoint that introduction into polysilane is relatively easy. Moreover, the vinyl monomer is relatively easy to synthesize and is usually commercially available and is convenient for commercialization.

  In the polysilane copolymer (b1), the vinyl monomer can be appropriately selected according to the type of the metal compound, the affinity for the metal fine particles (or the metal compound), and the like. Such a vinyl monomer is not particularly limited as long as it can form a copolymer with polysilane and has the affinity unit. Examples thereof include a nitrogen atom-containing monomer and an oxygen atom-containing monomer. And sulfur atom-containing monomers. Preferred vinyl monomers are selected from amide groups, amino groups (or substituted amino groups), nitrogen ring groups, acyl groups, alkoxy groups, ether groups (such as cyclic ether groups), carboxyl groups, thio groups, and sulfonic acid groups. And monomers having at least one kind of group (affinity group).

  The (meth) acrylic monomer having an affinity group or an affinity unit can be (1) relatively easy to control the copolymerization ratio (for example, the copolymerization ratio can be controlled by the irradiation amount of ultraviolet light). (2) It can be suitably used because it is excellent in that it can be obtained in a high yield, and (3) it can effectively protect metal fine particles (metal colloid).

  Examples of typical vinyl monomers (nitrogen atom-containing monomers, oxygen atom-containing monomers, sulfur atom-containing monomers) are shown below.

  The nitrogen atom-containing monomer includes an amide group-containing monomer, an amino group (or substituted amino group) -containing monomer, a nitrogen ring group-containing monomer, and the like.

Examples of the amide group-containing monomer include (meth) acrylamide monomers such as (meth) acrylamide, N-substituted (meth) acrylamide [for example, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) ) N-mono or di C _1-4 alkyl (meth) acrylamide] such as acrylamide, N, N-diethyl (meth) acrylamide], aminoalkyl (meth) acrylamide [for example, N, N-dimethylaminopropyl (meth) acrylamide N-mono or di C _1-4 alkylamino C _1-4 alkyl (meth) acrylamide etc.] and the like. (Meth) acrylamide monomers [particularly N, N-diC _1-4 alkyl (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide] are polysilanes Is highly reactive. In addition, when N, N-diC _1-4 alkyl (meth) acrylamide [in particular, N, N-dimethylacrylamide] is used, fine metal particles having a particle size of nanometer size (for example, 10 nm or less) and excellent dispersibility ( For example, gold nanoparticles can be efficiently generated.

Examples of the amino group (or substituted amino group) -containing monomer include amino group-containing (meth) acrylic monomers such as aminoalkyl (meth) acrylate [for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N-mono or di-C _1-4 alkylamino C _1-4 alkyl (meth) acrylate such as N, N-dimethylamino (meth) acrylate, etc.]; (meth) acryloyl Examples include morpholine.

  Examples of nitrogen ring group-containing monomers include cyclic amino groups such as vinyl monomers having a pyridine group (such as vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine) and vinyl monomers having a carbazole group (N-vinylcarbazole). Examples thereof include monomers. A vinyl monomer having a pyridine group is preferably used because it effectively adsorbs to metal atoms, particularly gold atoms, and stabilizes the generated gold nanoparticles. 2-Vinylpyridine and 4-vinylpyridine are commercially available, and it is possible to provide a copolymer with polysilane at low cost. In particular, 4-vinylpyridine can be uniformly dispersed on a polymer sheet and can be suitably used as described by Tanaka et al. In Langmuir, Vol. 19, page 3103 (2003). Moreover, the vinyl monomer which has a carbazole group has a tertiary amino group, and can protect metal microparticles (metal nanoparticles) effectively. In particular, since N-vinylcarbazole is commercially available and has photoconductivity, new photofunctionality can be imparted to metal fine particles (metal nanoparticles).

  Examples of the oxygen atom-containing monomer include acyl group-containing monomers, alkoxy group-containing monomers, ether group-containing monomers (such as cyclic ether group-containing monomers), and carboxyl group-containing monomers. .

Examples of the acyl group-containing monomer include acyl group-containing (meth) acrylic monomers such as acylacetoxyalkyl (meth) acrylate [for example, 2- (acetoacetoxy) ethyl (meth) acrylate (C _2- Examples include acylaceto group (2-acylaceto group) group-containing (meth) acrylic monomers such as ₄ acylacetyloxy) C _2-4 alkyl (meth) acrylate. A functional group that can be a ligand of a metal atom such as an acetoacetoxy group is effective because it chemically stabilizes metal fine particles (metal nanoparticles). In particular, 2- (acetoacetoxy) alkyl methacrylate can effectively coordinate to a metal atom and generate metal fine particles (metal nanoparticles) in a high yield. Moreover, since 2- (acetoacetoxy) ethyl methacrylate is marketed at a low price, it is easily industrialized or industrialized.

The alkoxy group-containing monomer includes a metal alkoxide-containing monomer, alkoxystyrene (for example, C _1-4 alkoxystyrene such as 4-methoxystyrene) and the like. Examples of the metal alkoxide-containing monomer include (meth) acryloyl group-containing alkoxysilanes such as dialkoxysilane having a (meth) acryloyl group (for example, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) (Meth) acryloyloxy C _2-4 alkyl C _1-4 alkyldiC _1-4 alkoxysilane such as acryloxypropylmethyldiethoxysilane), trialkoxysilane having a (meth) acryloyl group [for example, 2- (meta ) (Meth) acryloyloxy C _2-4 alkyltri C _1-4 alkoxysilane such as acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropyltriethoxysilane 3- (meth) acryloxypropyltris ( (Meth) acryloyloxy C _2-4 alkyl tri (C _1-4 alkoxy C _2-4 alkoxy) silane; N-(3- (meth) such as Tokishietokishi) silane acryloxy-2-hydroxypropyl) -3-amino [(Meth) acryloyloxy C _2-4 alkyl] amino C _2-4 alkyltrialkoxysilane etc.] such as propyltriethoxysilane.

  The (meth) acryl monomer containing a metal alkoxide can stabilize metal fine particles by coating the surface of metal fine particles (metal nanoparticles) with a metal oxide. Further, (meth) acryloyl group-containing alkoxysilanes (for example, methacryloxyalkylalkoxysilanes) can efficiently synthesize a block copolymer with polysilane by photopolymerization. For example, 3-methacryloxypropyltrialkoxysilane is commercially available. In particular, 3-methacryloxypropyltriethoxysilane has high storage stability of metal fine particles and is advantageous for industrialization or industrialization. Moreover, since the lone electron pair which exists in an oxygen molecule coordinates to alkoxy styrene in a metal microparticle (metal nanoparticle), a metal microparticle can be stabilized efficiently. Further, alkoxystyrene (such as 4-alkoxystyrene) can be suitably used because it is soluble in a solvent, and in particular, 4-methoxystyrene is commercially available and thus easily industrialized or industrialized.

Examples of the ether group-containing monomer include cyclic ether group-containing monomers (for example, vinyl monomers having a C _4-8 cyclic ether group such as 3-vinylbenzyltetrahydrofurfuryl ether). Such an ether group-containing monomer can stabilize metal fine particles efficiently because a lone pair present in oxygen molecules can be coordinated to metal fine particles (metal nanoparticles) in the same manner as alkoxystyrene. In particular, 3-vinylbenzyltetrahydrofurfuryl ether is commercially available and can be suitably used.

Examples of the carboxyl group-containing monomer include polymerizable unsaturated carboxylic acids (or salts thereof) such as alkene carboxylic acids (for example, C _3-6 alkene carboxylic acids such as (meth) acrylic acid, crotonic acid, and butenoic acid) ), Vinyl group-containing aromatic carboxylic acids (for example, vinyl C _6-10 aromatic carboxylic acids such as 4-vinylbenzoic acid) or salts thereof (alkali or alkaline earth metal salts such as sodium 4-vinylbenzoate) And the like. Such a carboxyl group-containing monomer can effectively adsorb metal atoms. Moreover, the vinyl monomer containing vinyl benzoic acid or vinyl benzoate can improve the developability at the time of patterning efficiently. In particular, 4-vinylbenzoic acid or sodium 4-vinylbenzoate is commercially available, and can provide a copolymer with polysilane at low cost. In addition, polyacrylic acid (or a salt thereof) is S.I. As described in Jolly et al., Langmuir, 16: 1354 (2000), it is possible to effectively capture silver nanoparticles and form a laminated film of silver nanoparticles on a polymer film. Therefore, when a polysilane compound having a polyacrylic acid unit is used, metal fine particles that can be used in an electronic device or the like can be suitably obtained.

  The oxygen atom-containing monomer may be a hydrosyl group-containing monomer or a monomer that generates a hydroxyl group by hydrolysis. For example, the polysilane copolymer (b1) may be a block copolymer of polyvinyl alcohol and polysilane (specifically, a saponified product of a block copolymer of vinyl acetate and polysilane). Such a vinyl alcohol unit can also stabilize metal fine particles (metal nanoparticles) efficiently.

As the sulfur atom-containing monomer, a thio group-containing monomer {alkylthioalkyl (meth) acrylate [for example, (C _1-4 alkylthio) C _1-4 alkyl (such as 2- (methylthio) ethyl (meth) acrylate) ( Thio group-containing (meth) acrylic monomers such as (meth) acrylate]}, sulfonic acid group-containing monomers (for example, styrene sulfonic acid (such as 4-styrene sulfonic acid)) and the like C _6-10 aromatic vinyl And a salt thereof (such as an alkali or alkaline earth metal salt such as sodium styrenesulfonate). Sulfur atoms can efficiently suppress aggregation of metal nanoparticles through chemical adsorption with metal atoms. Moreover, the (meth) acryl monomer (especially 2- (alkylthio) alkyl (meth) acrylate) containing a sulfur atom has high reactivity with polysilane, and can easily synthesize a copolymer with polysilane. In particular, 2- (alkylthio) alkyl (meth) acrylate is commercially available at a low price, and thus is easily industrialized. Moreover, the vinyl monomer which has a sulfonic acid or a sulfonate can adsorb | suck a metal atom effectively. In particular, styrene sulfonic acid or sodium styrene sulfonate effectively captures metal ions, particularly silver ions, and can be obtained at low cost.

  The vinyl monomers may be used alone or in combination of two or more.

  The polysilane copolymer (b1) may be a random copolymer, a block copolymer, an alternating copolymer, a comb copolymer or the like, but is usually a block copolymer [ie, polysilane (polysilane block) and In many cases, a polysilane block copolymer composed of a vinyl monomer block]. The structure of the block copolymer is not particularly limited, and may be a diblock structure, a triblock structure (ABA type, BAB type), or the like.

  In the polysilane copolymer (especially polysilane block polymer), the proportion of polysilane (or polysilane unit) is determined based on the constituent monomer of the polysilane copolymer [monomer constituting polysilane (or silicon atom constituting polysilane) and vinyl monomer It may be, for example, about 5 to 95 mol%, preferably 10 to 90 mol%, more preferably about 20 to 80 mol% (for example, 30 to 80 mol%) with respect to the whole.

  The number average molecular weight of the polysilane compound (polysilane, polysilane copolymer, etc.) may be, for example, 1000 to 100,000, preferably 2000 to 50000, and more preferably about 3000 to 30000. In the polysilane copolymer (polysilane block copolymer, etc.), the number average molecular weight of the polysilane (polysilane block, etc.) is, for example, about 300 to 50,000, preferably 500 to 40000, and more preferably about 1000 to 30000. May be.

  The polysilane compound can be prepared using various methods. The polysilane compound (a) (that is, polysilane) composed only of the polysilane unit is prepared in various manners using monomers having respective structural units (such as the units represented by the above formulas (1) to (3)) as raw materials. A method, for example, a method of dehalogenating polycondensation of halosilanes using magnesium as a reducing agent (“magnesium reduction method”, for example, International Publication No. WO 98/29476); dehalogenating of halosilanes in the presence of an alkali metal Polymerization methods (for example, “Kipping method” J. Am. Chem. Soc., 110, 124 (1988), Macromolecules, 23, 3423 (1990)); Dehalogenation condensation polymerization of halosilanes by electrode reduction (J Chem.Soc., Chem.Commun., 1161 (1 90), J. Chem. Soc., Chem. Commun., 897 (1992)): a method of dehydrogenating polycondensation of hydrosilanes in the presence of a metal catalyst (JP-A-4-334551); It can be prepared by a method based on anionic polymerization of disilylene (Macromolecules, 23, 4494 (1990)); a method based on ring-opening polymerization of cyclic silanes.

  Of the polysilanes represented by the formula (1), the cyclic polysilane may be obtained, for example, by cyclizing a part of the polysilane in the process of synthesizing the linear polysilane. Further, the cyclic polysilane may be obtained by an intramolecular cyclization reaction of the polysilane, for example, a method based on an intramolecular condensation reaction (such as an intramolecular dehalogenation reaction) in which polysilane ends self-condense. Furthermore, the polysilane whose end group is blocked can be prepared, for example, by reacting the polysilane prepared by the above-described method with a corresponding blocking agent (silyl compounds such as halosilanes, silyl triflates, and silanes). .

  Moreover, the preparation method of the polysilane compound (b) containing an affinity unit is not specifically limited, It can prepare using various synthetic chemistry methods. For example, the polysilane copolymer (b1) (polysilane block copolymer) is obtained by using polysilane (for example, polysilane prepared by the above-described method) as a photo-radical polymerization initiator of a vinyl monomer. A method of synthesizing a block copolymer with a vinyl monomer [(meth) acrylic monomer or the like] (for example, a method described in Polymer Vol. 43, page 1549) may be used. In particular, the (meth) acrylic monomer can be easily synthesized by photopolymerization of a block copolymer with polysilane. Such a method is simple and can be suitably used from an economical viewpoint.

  Furthermore, the polysilane (b2) to which the affinity unit is bonded is obtained by a method in which a monomer (silane compound) having a hydrophilic unit bonded to a silicon atom is used in advance in the preparation method of the polysilane, a reactive substituent (hydroxyl group) of the polysilane. And a compound having a functional group capable of forming a bond with the group and the affinity unit described above and a polysilane may be prepared by a method (chemical bond) using a conventional method.

[Metal compounds]
The metal compound is not particularly limited as long as it is a compound capable of generating the metal fine particles (or the metal constituting the metal fine particles) by reduction (that is, a metal compound in which the oxidation number of the metal atom is positive). In many cases.

Examples of such a metal compound (or metal salt) include metal oxide, metal hydroxide, metal halide (metal chloride, etc.), metal acid salt [metal inorganic acid salt (sulfate, nitrate, phosphoric acid). Salt, perchlorate, oxo acid salt such as hydrochloride), metal organic acid salt (such as acetate) and the like]. The form of the metal salt may be a single salt, a double salt, or a complex salt (electrolyte complex or non-electrolyte complex, usually an electrolyte complex), or a multimer (for example, a dimer). In addition, the metal compound (metal salt) includes, for example, an acid component [hydrogen chloride (HCl) and the like], a base component (ammonia and the like), water (H ₂ O) and the like (for example, a halogenated hydrogen compound, It may be a hydrate or hydrate). The metal compounds may be used alone or in combination of two or more.

  In addition, the metal compound is not particularly limited as long as metal fine particles can be generated, and can be composed of a metal (or metal atom). In the present invention, the metal compound can be suitably composed of Group 8-11 metals of the periodic table (that is, iron, ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, etc.), You may comprise noble metals (silver, gold, platinum, ruthenium, etc.). The metal compound may contain these metal atoms singly or in combination.

Specific examples of the metal compound include Group 8 to 11 metal compounds (or metal salts) of the periodic table, for example, Group 8 to 11 metal salts of the periodic table {inorganic acid salts [for example, noble metals such as silver nitrate (AgNO ₃ )]. Noble metal inorganic acid salts such as nitrates], organic acid salts [for example, noble metal acetates such as palladium acetate (Pd (CH ₃ CO ₂ ) ₂ etc.), ruthenium acetate ([Rh (CH ₃ CO ₂ ) ₂ ] ₂ etc.) Noble metal organic acid salts such as}, periodic group 8-11 metal halides {noble metal halides [eg, gold chloride (AuCl ₃ ), platinum chloride (PtCl ₂ , PtCl ₄ etc.), palladium chloride (PdCl ₂ etc.] Noble metal chlorides such as)], acid component-containing metals (such as periodic group 8-11 metals) halides [eg, chlorination such as chloroauric acid (HAuCl ₄ etc.), chloroplatinic acid (H ₂ PtCl ₆ etc.) You Hydrogen chloride-containing noble metal halides such as Shokusan], etc. These hydrates} and others.

  Below, typical metal compounds are illustrated about gold | metal | money, silver, copper, platinum, palladium, and rhodium among periodic table 11 group metals.

Gold compounds include gold halides (AuCl, AuCl ₃ , AuBr ₃ , AuI, AuI ₃ etc.), halogenated gold acids or their salts (HAuCl ₄ , HAuCl ₄ .4H ₂ O, NaAuCl ₄ .4H ₂ O, KAuCl. ₄ · 4H ₂ O, etc.), gold hydroxide (AuOH), gold cyanide (AuCN), such as gold oxide (Au ₂ O _3), gold sulfide _{(Au 2 S, Au 2 S} 3 (III) , such as such) An inorganic salt is mentioned. HAuCl ₄ .4H ₂ O is soluble in a polar organic solvent such as tetrahydrofuran (THF) and may be suitably used.

Silver compounds include inorganic salts [eg, silver halides such as AgF, AgCl, AgI, AgBr, silver oxides such as Ag ₂ O, Ag ₂ SO ₄ , AgS, AgCN, AgClO ₄ , Ag ₃ PO ₄ , AgSCN, _{AgNO 3, Ag 2 SO 3,} Ag 2 CO 3, Ag 2 CrO 4, Ag 2 Se, AgReO 4, AgBF 4, AgW 4 O 16, Ag 3 AsO 4, AgSbF 6, AgPF 6, AgHF 2, AgIO 3, Inorganic acid salts such as AgBrO ₃ , AgOCN, AgMnO ₄ and AgVO ₃ ], organic salts (or complexes) [for example, C ₆ H ₅ CO ₂ Ag, C ₆ H ₁₁ (CH ₂ ) ₃ CO ₂ Ag, CH ₃ CH (OH) CO ₂ Ag, silver trifluoroacetate (CF ₃ CO ₂ Ag), C ₂ F ₅ CO ₂ Ag, C ₃ F ₇ CO ₂ Ag, AgO ₂ CCH ₂ C (OH) (CO ₂ Ag) CH ₂ Carboxylates such as CO ₂ Ag, sulfonates such as silver p-toluenesulfonate, silver trifluoromethanesulfonate (CF ₃ SO ₃ Ag), (CH ₃ COCH═C (O—) CH ₃ ) Ag, ( C ₂ H ₅ ) ₂ NCS ₂ Ag, etc.]. Silver nitrate (AgNO ₃ ) can be obtained at a low cost and can be suitably used.

Examples of the copper compound include inorganic salts [for example, Cu ₂ O, CuO, Cu (OH) ₂ , CuF ₂ , CuCl, CuCl ₂ , CuBr, CuBr ₂ , CuI, and other copper halides, CuCO ₃ , CuCN, Cu (NO _{3) 2, Cu (ClO 4} ) 2, Cu 2 P 2 O 7, Cu 2 Se, CuSe, CuSeO 3, CuSO 4, Cu 2 S, CuS, Cu (BF 4) 2, Cu 2 HgI 4, CuSCN, Inorganic acid salts such as (CF ₃ CO ₂ ) ₂ Cu, (CF ₃ SO ₃ ) ₂ Cu, CuWO ₄ , Cu ₂ (OH) PO ₄ ], organic salts (or complexes) [for example, copper (I) acetate , Copper (II) acetate, [C ₆ H ₁₁ (CH ₂ ) ₃ CO ₂ ] ₂ Cu, [CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CO ₂ ] ₂ Cu, (HCO ₂ ) ₂ Cu _{, [HOCH 2 [CH (OH} )] 4 CO 2] carboxylic such as ₂ Cu _{Salt, (CH 3 COCH = C (} O-) CH 3) Cu, CH 3 (CH 2) 3 SCu, and the like (CH ₃ O), such as ₂ Cu]. Copper acetate is soluble in a polar organic solvent such as tetrahydrofuran (THF) and can be suitably used.

Platinum compounds include inorganic salts [for example, platinum halides such as PtO ₂ , PtCl ₂ , PtCl ₄ , PtBr ₂ , PtBr ₄ , PtI ₂ , PtI ₅ , halogenated platinic acids such as HPtCl ₆ · 2H ₂ O, PtS ₂ , Pt (CN) ₂ etc.], organic salts (or complexes) [eg (CH ₃ COCH═C (O—) CH ₃ ) Pt, (C ₆ H ₅ CN) ₂ PtCl ₂ etc.], etc. . Note that HPtCl ₆ · 2H ₂ O is soluble in a polar organic solvent such as tetrahydrofuran (THF) and can be suitably used.

Examples of the palladium compound include inorganic salts [eg, palladium halides such as PdO, PdCl ₂ , PdBr ₂ , PdI ₂ , PdCN ₂ , Pd (NO ₃ ) ₂ , PdS, PdSO ₄ , K ₂ Pd (S ₂ O ₃ ) ₂ · H ₂ O, chloropalladic acid, etc.], organic salts (or complexes) [for example, carboxylates such as Pd (CH ₃ CO ₂ ), palladium (II) propionate, (CF ₃ CO ₂ ) ₂ Pd , (CH ₃ COCH═C (O—) CH ₃ ) Pd, (C ₆ H ₅ CN) ₂ PdCl _2, etc.]. Pd (CH ₃ CO ₂ ) ₂ is soluble in a polar organic solvent such as tetrahydrofuran (THF) and can be suitably used.

Examples of the rhodium compound include inorganic salts [eg, rhodium halides such as Rh ₂ O ₃ , RhO ₃ , RhCl ₃ , RhBr ₃ , RhI ₃ , RhPO ₄ , Rh ₂ SO _4, etc.], organic salts (or complexes) [eg, , Rh (CH ₃ CO ₂ ) ₂ , (CF ₃ CO ₂ ) ₂ Rh, {[CH ₃ (CH ₂ ) ₆ CO ₂ ] ₂ Rh} ₂ , [(CF ₃ CF ₂ CF ₂ CO ₂ ) ₂ Rh] ₂ , carboxylic acid salts such as {[(CH ₃ ) ₃ CCO ₂ ] ₂ Rh} ₂ , (CH ₃ COCH═C (O—) CH ₃ ) Rh, etc.] and the like. Rh (CH ₃ CO ₂ ) ₂ is soluble in a polar organic solvent such as tetrahydrofuran (THF) and can be suitably used.

  Among these metal compounds, in particular, a metal chloride chloride {hydrogen chloride-containing metal chloride represented by the formula: ACln · [HCl] m (where A is a metal atom, m, and n are positive integers)}, etc. Since the acid component-containing metal compounds (metal halides such as metal chlorides, especially noble metal chlorides) are metal compounds that are easily reduced, coupled with the high reducing action of polysilane compounds, the generation rate of metal fine particles is further increased. Metal fine particles having high stability (stability over time) can be generated.

  In the composition of the present invention, the ratio of the metal compound depends on the resolution and molecular weight of the polysilane compound, but is, for example, 0.5 to 500 parts by weight, preferably 1 to 400 parts per 100 parts by weight of the polysilane compound. It may be about 2 parts by weight, more preferably about 2 to 200 parts by weight (for example, 5 to 150 parts by weight).

  The composition of the present invention can also be used as a coating composition (coating solution). The coating composition may be composed of the polysilane compound and the metal compound, and may be a solventless coating composition (coating agent) or a coating composition (coating agent) containing a solvent. A preferred coating composition is a composition (or coating solution) containing a solvent. As the solvent, a solvent capable of dissolving or dispersing (particularly dissolving) a polysilane compound and a metal compound can be used. Such a solvent can be appropriately selected according to the type of polysilane compound and metal compound. For example, alcohols (alkyl alcohols such as methanol, ethanol, propanol, isopropanol, butanol and isobutanol), ethers (dimethyl ether) , Chain ethers such as diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran), esters (such as acetates such as methyl acetate, ethyl acetate and butyl acetate), ketones (such as acetone and ethyl methyl ketone) Dialkyl ketones), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, cellosolve acetate, butoxycarbitol acetate Cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), carbitols (carbitol, etc.), halogenated hydrocarbons (methylene chloride, chloroform, etc.), acetals (acetal, methylal, etc.), amides (Dimethylformamide etc.), sulfoxides (dimethylsulfoxide etc.), nitriles (acetonitrile, benzonitrile etc.) and the like. These solvents may be used alone or in combination of two or more.

  The ratio of the solvent may be, for example, 10 to 50000 parts by weight, preferably 30 to 10000 parts by weight, and more preferably about 50 to 5000 parts by weight with respect to 100 parts by weight of the polysilane derivative.

  In addition, when a solvent is included, the composition or the coating liquid may be in the form of a solution or in the form of a dispersion.

  The composition of the present invention may contain a silane coupling agent, a surfactant (such as a silicone-based or fluorine-based surfactant), and the like. When such an additive is added, as will be described later, in the case of using the composition of the present invention for application to a substrate (such as a glass substrate), the adhesion to the substrate is efficiently improved, or a coating solution The uneven evaporation of the solvent can be reduced, and the smoothness and flatness of the coating can be improved efficiently.

  Furthermore, the composition of this invention may contain components, such as a sensitizer and a leveling agent. Sensitizers include silicone resins, radical generators (photo radical generators) [peroxides (organic peroxides such as hydrogen peroxide (hydrogen peroxide)) and benzoyl peroxide), azobisisobutyro Azo compounds such as nitrile, persulfates such as ammonium persulfate, organic sulfur compounds such as dibutyl sulfide, radical generators capable of generating halogen radicals (2,4,6-tris (trihalomethyl) -1,3,5- Triazines, etc.], oxidizing agents (amine oxide, phosphine oxide, etc.), acetophenone compounds (diethoxyacetophenone, etc.), benzophenone compounds (benzophenone, etc.), benzoin compounds (benzoin ethyl ether, etc.), benzyl compounds (benzyl etc.) ), Anthraquinone compounds (such as anthraquinone) The sensitizers may be used alone or in combination of two or more thereof, and the sensitizers described in JP-A-8-262728 and Japanese Patent No. 3274918 are used as sensitizers for polysilane. (Photo radical generators, oxidizing agents, etc.) may be preferably used.By adding such components, the decomposition sensitivity (decomposability) of the polysilane compound can be further enhanced. Or leveling agent) is, for example, about 0.1 to 20 parts by weight, preferably about 0.5 to 10 parts by weight, and more preferably about 1 to 5 parts by weight with respect to 100 parts by weight of the polysilane compound. Also good.

  In addition, the composition (polysilane composition) of this invention may contain various additives suitably according to a use (For example, a use as a photosensitive resin composition as mentioned later). Examples of such additives include antifoaming agents, coating improvers, thickeners, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, surfactants, and dissolution agents. Accelerators, colorants, fillers, antistatic agents, gelling agents and the like can be exemplified. The additives (silane coupling agent, sensitizer, stabilizer, etc.) may be used alone or in combination of two or more.

  In addition, the composition of the present invention is not limited to the production of fine metal particles and the reduction performance of the polysilane compound, and other reducing agents (such as conventional reducing agents such as sodium borohydride), metal compounds (or metals) A compound having affinity for (fine particles) (resin such as polyvinyl pyrrolidone and polyvinyl alcohol) may be included. In the composition of the present invention, the polysilane compound has an excellent reducing ability and has an affinity for the metal compound (and the generated metal fine particles), and thus has such a reducing agent and affinity. Even if it does not contain a compound, fine metal particles can be produced efficiently.

  The form of the composition of the present invention is not particularly limited, and may be, for example, a granular form (or a granular mixture), and may be a coating composition (application liquid) as described above. . The said composition (coating composition) can obtain a coating film by apply | coating on a board | substrate (The board | substrate etc. which are mentioned later).

  In addition, the composition of this invention can be prepared by mixing a conventional method, for example, the said polysilane compound, the said metal compound, and another component (a solvent, a sensitizer, etc.) as needed. For example, the composition of the present invention may be prepared by mixing (dissolving or dispersing) a polysilane compound, the metal compound and [if necessary, other components (such as a sensitizer)] in a solvent. .

[Metal fine particles and method for producing the same]
As described above, the composition of the present invention can be suitably used for the production of metal fine particles (or metal colloids). That is, in the present invention, the polysilane compound of the composition is decomposed [specifically, radicals (silyl radicals are generated by decomposition)] to generate metal fine particles (metal fine particles corresponding to the metal compound). be able to. The generated metal fine particles may be a mixture with a solvent, and the form of the mixture is, for example, a solution dissolved in a solvent (such as the solvent exemplified above) or dispersed in a solvent (such as the solvent exemplified above). It may be a dispersed liquid.

  The principle that metal fine particles are generated by the decomposition of the polysilane compound is considered as follows. The polysilane constituting the polysilane compound has delocalized electrons due to sigma conjugation in its main chain, so it is decomposed by irradiation with active energy rays to generate radicals (silyl radicals), and this active species (radicals) Shows a reducing action. That is, by utilizing the “photoreducibility” of this active species, the metal compound is reduced in a relatively short time to produce metal fine particles.

  In the method for producing such metal fine particles, the method for decomposing the polysilane compound is not particularly limited as long as the polysilane compound is decomposed to generate radicals. Usually, an active energy ray is allowed to act on the composition (or Can be decomposed by irradiation).

  The active energy ray is not particularly limited as long as it has sufficient energy to excite and decompose the polysilane (compound). For example, active ray (or ray), heat ray (infrared ray or heat energy), etc. Can be mentioned. Examples of actinic rays (or light sources) include visible rays, ultraviolet rays (near ultraviolet rays, far ultraviolet rays, vacuum ultraviolet rays, etc.), X-rays, and the like. Of these actinic rays, ultraviolet rays are preferred. The actinic ray may be a single wavelength, a composite wavelength, or a mixed wavelength.

Examples of the active light source to be acted on (or irradiated) include halogen lamps, mercury lamps (low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, etc.), deuterium lamps, UV lamps, lasers {eg, helium − Cadmium laser, excimer laser [for example, XeCl (308 nm), KrF (248 nm), KrCl (222 nm), ArF (193 nm), ArCl (172 nm), F ₂ (157 nm), etc.], etc.], etc.] can be exemplified.

The irradiation (or exposure) energy is not particularly limited, but may be usually about 1 mJ / cm ^{2 to} 100 J / cm ² , preferably about 10 mJ / cm ^{2 to} 10 J / cm ² . The exposure time can be selected from the range of about 0.005 seconds to 10 minutes, for example, 0.01 seconds to 1 minute, preferably 0.1 to 30 seconds, more preferably about 1 to 20 seconds. You can choose.

  Moreover, when making a heat ray act, the temperature (heating temperature) made to act on the said composition may be 30-200 degreeC, for example, Preferably it is 40-150 degreeC, More preferably, about 40-100 degreeC may be sufficient.

  The active energy rays may be used alone or in combination of two or more. In particular, the combination of actinic rays (particularly ultraviolet rays) and heat rays can further increase the production rate and curing rate of metal fine particles more efficiently. Examples of a method of combining actinic rays and heat rays include a method of heating the composition and irradiating actinic rays, a method of irradiating actinic rays and then heating.

  In the metal fine particles (solution or dispersion containing metal fine particles) obtained by such a method, a decomposition product after radical generation of the polysilane compound is present on the surface of the metal fine particles (or the surface of the metal fine particles is protected. ) Because of this, stability or storage stability is high. In particular, when the polysilane compound is a polysilane compound (such as the polysilane copolymer) having the affinity group (or affinity unit), the metal fine particles are not only decomposed by the polysilane but also by the affinity group. Because of stabilization or protection, the aggregation of metal fine particles can be suppressed at a high level, and the stability (long-term stability, environmental stability) or storage stability (or long-term storage stability) of metal fine particles is extremely high.

  The particle size (average particle size) of the metal fine particles of the present invention is several nm (for example, 1 nm) to several μm (for example, 5 μm) depending on the type of polysilane compound (the type of the affinity unit and the presence or absence thereof). For example, it may be 1 to 3000 nm, preferably 1 to 2000 nm, and more preferably about 1 to 1500 nm. In particular, in the present invention, nanoparticles (metal nanoparticles), for example, a particle size (or average particle size) of 1 to 1000 nm (for example, 1 to 800 nm), preferably 1 to 500 nm (for example, 1 to 300 nm), More preferably, even fine metal particles of about 1 to 200 nm (for example, 1 to 150 nm), particularly about 1 to 50 nm (for example, 1 to 30 nm) can be efficiently generated (prepared).

  The method of the present invention (metal fine particle production method) can be applied to various uses. For example, the composition of the present invention may be used as a photosensitive resin composition (negative photosensitive resin composition).

  Specifically, the composition (for example, a coating liquid composed of a polysilane compound, a metal compound, and a solvent) is applied to a substrate, exposed to generate metal fine particles, and further developed to develop metal fine particles. A pattern (negative pattern) including That is, in such a pattern forming method, a metal compound that is soluble in the developer is changed to insoluble in the developer by exposure (reduction). Specifically, when the composition is applied to a substrate to form a coating film, and then exposure (light irradiation) is performed, generation of metal fine particles and curing by photocrosslinking occur simultaneously or continuously by light irradiation. When development is performed later, the unexposed portion is dissolved and removed, and a negative pattern containing metal fine particles (nanoparticles) is formed.

  It does not specifically limit as a board | substrate, For example, metals, such as a silicon wafer and aluminum, a plastics, glass, ceramics etc. can be illustrated. The substrate may be subjected to surface treatment (surface treatment with a silane coupling agent or the like, coating treatment with an anchor coating agent or the like). Because the composition (photosensitive composition) of the present invention is composed of a polysilane compound (and a metal compound), it has high adhesion to a substrate (for example, an inorganic substrate such as a glass substrate) and is simple and efficient. A pattern can be formed.

  Although the said photosensitive resin composition is based also on the apply | coating method, you may comprise at least a polysilane compound, a metal compound, and a solvent, for example. In the photosensitive resin composition, the solvent may be any of the solvents exemplified above, and in particular, each component contained in the composition can be dissolved or uniformly dispersed well, and smooth and free from evaporation unevenness. It is preferable that a flat coating film can be formed, and that good storage stability can be given. Examples of such solvents include ethers, acetals, ketones, esters and the like. In the photosensitive resin composition, the solid content (polysilane compound, metal compound, etc.) concentration is not particularly limited as long as the solid content (polysilane compound, metal compound, etc.) can be dissolved, and the coating method, coating thickness, etc. It can be adjusted appropriately according to In addition, the photosensitive resin composition contains conventional resins [photosensitive resin (negative photosensitive resin), binder resin, etc.] used in the photosensitive resin composition as necessary in order to improve film formability. You may do it.

  The method of applying the composition to the substrate is not particularly limited as long as a film can be formed. Conventional coating methods such as spin coating (rotary coating), roll coating, curtain coating, and dip coating are used. , Cast method etc. can be used. As the coating device, a device corresponding to the above coating method, for example, a spin coater, a slit coater, a roll coater, a bar coater or the like can be used. If necessary, the substrate may be dried after application, or the substrate may be pre-baked using a hot plate or the like.

  In the coating film obtained by applying the composition, the thickness of the coating film is not particularly limited, and is, for example, 0.01 to 50 μm, preferably 0.01 to 20 μm, more preferably about 0.01 to 5 μm. It may be.

  The exposure can be performed by irradiating actinic rays (for example, ultraviolet rays) as described above, and the exposure (irradiation) energy can be appropriately selected from the same range as described above. In the present invention, since the polysilane compound has high degradability (or reducibility or photosensitivity), even with an exposure time of a relatively short time (for example, about 1 to 20 seconds), it can be easily formed with high pattern formation. And a pattern can be formed efficiently. The exposure may be performed through a mask or without a mask. The mask is not particularly limited as long as it is a mask used in ordinary photolithography, but a chromium mask is effective for exposure with ultraviolet rays, and molybdenum or the like is used when a vacuum ultraviolet light source is used. A mask using the configured reflection type mirror may be preferably used. When a mask is not used, exposure (active energy ray irradiation) may be performed with a laser or electron beam direct drawing device, and a pattern may be directly irradiated (or a pattern is formed) to the substrate. In addition, you may heat-process (post-exposure baking, PEB) after exposure as needed. The temperature of the heating (PEB) may be about 50 to 150 ° C., preferably 60 to 150 ° C. (for example, 60 to 140 ° C.), more preferably about 70 to 150 ° C. (for example, 70 to 130 ° C.).

  After exposure, a negative pattern shaped product of the metal fine particles (metal nanoparticles) can be obtained by removing the non-irradiated portion of the active light beam using a developer. The developer (or developer) used for development can be appropriately selected according to the type of the photosensitive resin composition (type of polysilane compound, etc.). The developer is not particularly limited as long as the unexposed part can be dissolved. For example, (alcohols such as methanol, ethanol, isopropanol), ketones (methyl ethyl ketone, methyl isobutyl ketone, etc.), ethers (dioxane, tetrahydrofuran) Etc.), cellosolves, cellosolve acetates and the like can be exemplified, and these can be used alone or in admixture of two or more. The development method is not particularly limited, and for example, a paddle (meniscus) method, a dip method, a spray method, or the like can be used. By such a series of processes, the exposed portion is cured and the unexposed portion is dissolved in the developer, and a negative pattern of metal fine particles (composition) is produced. In addition, in order to complete hardening after image development, you may heat-process (heat processing) as needed.

  The composition of the present invention is useful for producing metal fine particles (particularly metal nanoparticles). In particular, a metal fine particle can be generated by a simple method such as applying an active energy ray without using a general-purpose reducing agent or an organic compound having a protective group, etc. It is useful above. Therefore, the fine metal particles (and their negative patterns) obtained by the method of the present invention are used in the optical field (for example, single-electron transistors in the quantum electronics field, nonlinear optical elements in the optical information processing field), color former (coloring material). (For example, coloring materials such as paint inks and color filters for displays, etc.) and biotechnology (such as an adsorbent carrier for immunological test materials in the field of clinical examination and biochemical sample measurement). In particular, the pattern (negative pattern) obtained by the method of the present invention not only has high adhesion to the substrate, but also has high transparency and conductivity, and can be suitably used for optical devices (electrodes, circuits, etc.). .

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
Poly (methylphenylsilane) (PMPS) (number average molecular weight Mn = 2.6 × 10 ⁴ ) synthesized by Wurtz coupling reaction (method described in RDMiller and J. Michi, Chem. Rev., 89, 1359 (1989)) 20 mg of molecular weight distribution Mw / Mn = 2.8) and 2 mg of chloroauric acid (HAuCl ₄ ) were dissolved in 2 mL of tetrahydrofuran (THF). When this THF solution was irradiated with ultraviolet light at an energy of 1 J / cm ² using a high-pressure mercury lamp (“USHIO SP-V” manufactured by USHIO INC.), A large number of black nanoparticles (particles) The diameter was about several hundred nm).

(Example 2)
Polymer, Volume 43, page 1549, by block copolymer of PMPS and N, N-dimethylacrylamide (DMAA) [P (MPS-co-DMAA)] (number average molecular weight Mn = 1.7 × 10 ⁴ , Molecular weight distribution Mw / Mn = 1.8, methylphenylsilane (MPS) unit number = 108, DMAA unit number = 135). 5 mg of silver nitrate (AgNO ₃ ) was placed in 1 mL of isopropyl alcohol (IPA) and dissolved by stirring at 50 ° C. While heating this AgNO ₃ / IPA solution to 50 ° C., a solution of 1 mL of THF containing 20 mg of P (MPS-co-DMAA) was added dropwise. When this THF solution was added, the AgNO ₃ / IPA solution immediately turned from pale yellow to brown, and when heating at 50 ° C. was continued, it turned amber after about 30 minutes. When the ultraviolet-visible absorption spectrum of the obtained solution was measured, plasmon absorption by silver nanoparticles was confirmed in the vicinity of 400 nm.

Example 3
20 mg of the polysilane copolymer [P (MPS-co-DMAA)] obtained in Example 2 and 2 mg of chloroauric acid (HAuCl ₄ ) were dissolved in 2 mL of THF and stirred for 2 hours. The color of the THF solution did not change from yellow even by such stirring, and partial aggregation (or formation) of gold nanoparticles as in Example 1 was suppressed. When this THF solution was irradiated with ultraviolet rays at an energy of 1 J / cm ² using a high-pressure mercury lamp (“USHIO SP-V” manufactured by USHIO INC.), The color of the solution changed from yellow to red. When the ultraviolet-visible absorption spectrum of the obtained solution was measured, plasmon absorption by gold nanoparticles was confirmed in the vicinity of 525 nm. FIG. 1 shows an ultraviolet-visible absorption spectrum of the obtained gold nanoparticles (THF solution containing gold nanoparticles). Thus, in Example 3, aggregation of gold nanoparticles was suppressed as compared with the case where PMPS was used.

  Further, from the result of transmission electron microscope (TEM) image and light scattering measurement, it was confirmed that the generated gold nanoparticles had a particle size of about 5 nm. FIG. 2 shows a transmission electron microscope (TEM) image (photograph) of the obtained gold nanoparticles. Furthermore, although the obtained gold nanoparticle was preserve | saved for three months, the extreme aggregation of the gold nanoparticle did not occur.

Example 4
Polymer, Volume 43, page 1549, a block copolymer of PMPS and 2- (acetoacetoxy) ethyl methacrylate (AAEM) [P (MPS-co-AAEM)] (number average molecular weight Mn = 2) 1 × 10 ⁴ , molecular weight distribution Mw / Mn = 2.2, methylphenylsilane (MPS) unit number = 172, AAEM unit number = 64) 20 mg and chloroauric acid (HAuCl ₄ ) 2 mg were dissolved in 2 mL of THF, Stir for 2 hours. The color of the THF solution did not change from yellow as agglomeration of gold as in Example 1 was suppressed even by such stirring. When this THF solution was irradiated with ultraviolet rays at an energy of 1 J / cm ² using a high-pressure mercury lamp (“USHIO SP-V” manufactured by USHIO INC.), The color of the solution changed from yellow to red. When the ultraviolet-visible absorption spectrum of the obtained solution was measured, the absorption by the plasmon of the gold nanoparticle was observed at 530 nm. Moreover, it was confirmed from the result of the transmission electron microscope (TEM) and the light scattering measurement that the particle size of the generated gold nanoparticles is about 10 nm.

(Example 5)
Polymer, Volume 43, page 1549, a block copolymer of PMPS and 2- (methylthio) ethyl methacrylate (MTEM) [P (MPS-co-MTEM)] (number average molecular weight Mn = 8.3 × 10 ³ , molecular weight distribution Mw / Mn = 1.6, methylphenylsilane (MPS) unit number = 63, MTEM unit number = 21) 20 mg and chloroauric acid (HAuCl ₄ ) 2 mg were dissolved in 2 mL of THF, Stir for 2 hours. The color of the THF solution did not change from yellow as agglomeration of gold as in Example 1 was suppressed even by such stirring. When this THF solution was irradiated with ultraviolet light at an energy of 1 J / cm ² using a high pressure mercury lamp (USHIO SP-V, manufactured by USHIO INC.), The color of the solution changed from yellow to reddish orange. Moreover, from the result of the transmission electron microscope (TEM) and the light scattering measurement, it was confirmed that the particle diameter of the generated gold nanoparticles was about 100 nm.

(Example 6)
2 mg of P (MPS-co-DMAA) and chloroplatinic acid (H ₂ PtCl ₆ ), which are polysilane copolymers obtained in Example 2, were dissolved in 2 mL of THF and stirred for 2 hours. The color of the THF solution did not change from yellow as agglomeration of platinum as in Example 1 was suppressed even by such stirring. When this THF solution was irradiated with ultraviolet light at an energy of 1 J / cm ² using a high pressure mercury lamp (USHIO SP-V, manufactured by USHIO INC.), The color of the solution changed from yellow to ocher. Moreover, it was confirmed from the result of the transmission electron microscope (TEM) that the particle size of the platinum nanoparticles generated is 100 to 200 nm.

(Example 7)
The THF solution containing P (MPS-co-DMAA) and chloroauric acid (HAuCl ₄ ) obtained in Example 3 was spin-coated on a glass substrate under the conditions of 2000 rpm for 30 seconds. A substrate coated with this THF solution was passed through a chromium mask having a comb pattern of 100 μm, using a high pressure mercury lamp (USHIO SP-V, manufactured by USHIO INC.), Conditions of 140 mW / cm ² for 7 seconds. And exposed. The substrate is heated at 120 ° C. for 30 minutes and then developed with an IPA / methyl isobutyl ketone (MIBK) mixed solution (IPA / MIBK (volume ratio) = 2/1) to contain gold nanoparticles. A 100 μm comb pattern was obtained. FIG. 3 shows a transmission electron microscope (TEM) photograph of the obtained comb pattern.

(Example 8)
Polymer, Volume 43, page 1549, PMPS synthesized by block copolymer and 2- (acetoacetoxy) ethyl methacrylate (AAEM) block copolymer (P (MPS-co-AAEM)) (number average molecular weight Mn = 2) 0.1 × 10 ⁴ , molecular weight distribution Mw / Mn = 2.2, number of units of methylphenylsilane (MPS) = 172, number of units of AAEM = 64) 20 mg and palladium acetate [Pd (CH ₃ CO ₂ ) ₂ ] 2 mg in 2 ml of THF And stirred for 1 hour. With stirring, the color of the THF solution changed from brown to dark brown. The THF solution was irradiated with ultraviolet rays at an energy of 1 J / cm ² using a high-pressure mercury lamp (USHIO SP-V, manufactured by USHIO INC.) To decompose the polysilane to obtain palladium nanoparticles. . From the result of transmission electron microscope (TEM), it was confirmed that the particle diameter of the palladium nanoparticles produced was about 5 nm. The THF solution was spin coated on a glass substrate. Subsequently, after irradiation with ultraviolet light (300 mJ / cm ² ) through a chromium mask having 100 μm L & S (line and space), development was performed with hexane, a negative palladium pattern of 100 μm L & S was formed.

Example 9
Rhodium nanoparticles were obtained in the same manner as in Example 8, except that palladium acetate was replaced with rhodium acetate [Rh (CH ₃ CO ₂ ) ₂ ]. From the result of transmission electron microscope (TEM), it was confirmed that the particle size of the rhodium nanoparticles produced was about 10 nm.

(Example 10)
P (MPS-co-AAEM) is a block copolymer of PMPS and 3-methacryloxypropyltriethoxysilane (number average molecular weight Mn = 1.5 × 10 ⁴ , number of units of methylphenylsilane (MPS) = 140, 3 -Gold nanoparticles were obtained in the same manner as in Example 3 except that the number of units of methacryloxypropyltriethoxysilane was changed to 30). From the result of the transmission electron microscope (TEM), it was confirmed that the particle size of the gold nanoparticles generated was about 50 nm.

FIG. 1 is an ultraviolet-visible absorption spectrum of a THF solution containing gold nanoparticles obtained in Example 3. FIG. 2 is a transmission electron microscope (TEM) photograph of the gold nanoparticles obtained in Example 3. FIG. 3 is a transmission electron microscope (TEM) photograph of the comb pattern obtained in Example 7.

Claims (13)

  A composition for producing metal fine particles, comprising a polysilane compound and a metal compound capable of producing the metal fine particles by reduction.   The composition according to claim 1, wherein the polysilane compound is a copolymer of polysilane and a vinyl monomer containing a unit having affinity for the metal compound and / or metal fine particles.   The vinyl monomer is a monomer having at least one group selected from an amide group, an amino group, a nitrogen ring group, an acyl group, an alkoxy group, an ether group, a carboxyl group, a thio group, and a sulfonic acid group. The composition according to claim 2.   The composition according to claim 1, wherein the metal compound comprises a Group 8-11 metal of the periodic table.   The composition according to claim 1, wherein the metal compound is a chlorinated noble metal acid.   The composition according to claim 1, wherein the ratio of the metal compound is 1 to 400 parts by weight with respect to 100 parts by weight of the polysilane compound.   The coating film obtained by apply | coating the composition of Claim 1 on a board | substrate.   A method of producing metal fine particles by decomposing a polysilane compound by applying an active energy ray to the composition according to claim 1.   The method according to claim 8, wherein the active energy ray is at least one selected from ultraviolet rays and heat rays.   The method according to claim 8, wherein the composition according to claim 1 is applied to a substrate, exposed to form metal fine particles, and further developed to form a pattern containing the metal fine particles.   Metal fine particles obtained by the method according to claim 8.   The metal fine particle according to claim 11, which is a nanoparticle.   A pattern obtained by the method of claim 10.