JP2003327638A - Solid with polymer chain-modified surface and production method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid having the following characteristics: the surface is highly and permanently hydrophilic, the surface is composed of separated hydrophilic and hydrophobic parts, the surface has etching resistance, and the like; and to provide a production method for the same having the above- mentioned surface characteristics. <P>SOLUTION: The solid with the polymer chain-modified surface, is obtained by grafting a polymer chain containing a constitutional unit based on an α, β-unsaturated monomer (a) having an organic group (a1) represented by formula (1), through a polymerization-initiating group introduced into the polymer surface (in formula (1), R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each hydrogen atom or a 1-18C organic group; R<SP>4</SP>is a 1-18C organic group, and R<SP>3</SP>and R<SP>4</SP>may be bonded to each other to form a heterocyclic ring containing Y as a hetero atom; and Y is oxygen or sulfur atom). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is highly applicable to fields in which a hydrophilic surface, a surface having both hydrophilic and hydrophobic properties separated, a surface having resistance to various kinds of etching, etc. are used as a function. A molecular chain-modified surface solid and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, modification has been attempted to impart various functions to the surface of a material. Graft polymerization on a solid surface is one of the widely adopted surface modification methods. In this surface graft, it has been proposed to introduce a polymerization initiating group into the solid surface in advance, but in the conventional technology, the surface graft density is controlled and the primary structure of the graft chain (molecular weight, molecular weight distribution) is controlled. However, there is a problem that it is difficult to control the (monomer arrangement pattern) and the like, and it is also difficult to form the graft surface on a predetermined patterned region.
The present inventors have conducted studies to solve these problems,
Japanese Patent Laid-Open No. 11-263819 and Synthetic Fiber Lecture No. 56
On pages 9 to 14 (7 (November, 1999)), a surface solid in which a graft chain having a highly controlled primary structure is densely bonded by making full use of a specific polymerization initiation group and a living radical polymerization method. It was also proposed that the grafted chains could be patterned to obtain bound surface solids.

On the other hand, different characteristics are required for solid surfaces for various uses. For example, a hydrophilic surface is necessary for developing antistatic properties, antifogging properties, etc. in a transparent film, etc., and a hydrophilic surface may be required when imparting biocompatibility to medical materials. . further,
The surface where both hydrophilic and hydrophobic properties exist separately is a property required for materials such as printing plates. A surface having etching resistance is an essential property for semiconductor-related materials and materials that require various patterning. In order to develop these practical properties permanently and at a higher level,
Japanese Patent Application Laid-Open No. 11-26381 discloses a method in which graft chains having a precisely controlled primary structure are densely bound to the surface of a solid.
In addition to the proposal of Japanese Patent Publication No. 9, it is necessary to further optimize the graft chain composition for imparting hydrophilicity, develop a method for separating hydrophilic / hydrophobic and allow them to exist on the surface, and a method for expressing etching resistance. Met.

[0004]

The present invention has been made in view of the above problems. That is, the first object of the present invention is to provide a solid having characteristics such as a higher and permanent hydrophilic surface, a surface having hydrophilic and hydrophobic sites separated from each other, and a surface having etching resistance. Especially.
A second object of the present invention is to provide a method for producing a solid having the above-mentioned surface characteristics.

[0005]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have introduced a specific polymerization initiation group, and have a structural unit based on a monomer having a specific group on a solid surface. In addition, the present inventors have found that grafting via the above-mentioned polymerization initiation group has an excellent effect on the above-mentioned properties and the like, and have completed the present invention. That is, the present invention is the following [1] to [12]. [1] The side chain has the following formula (1)

[0006]

[Chemical 7]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atom.
In the organic functional group of 8, R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. ) Organic group (a1)
And a polymer chain containing a structural unit based on the α, β-unsaturated monomer (a) having a group is grafted via a polymerization initiation group introduced on the solid surface. Polymer chain modified surface solid.

[2] The side chain in the polymer chain of the above [1] is represented by the following formula (1)

[0009]

[Chemical 8]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
In the organic functional group of 8, R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. (3) A polymer chain-modified surface solid obtained by converting a part or all of the organic group represented by (4) to a carboxyl group or a carboxyl group by hydrolysis or heating reaction.

[3] The side chain has the following formula (1)

[0012]

[Chemical 9]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
In the organic functional group of 8, R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. ) Organic group (a1)
To an α, β-unsaturated monomer (b) having a structural unit (A) based on an α, β-unsaturated monomer (a) having a group and an organic group (b1) having reactivity with a carboxyl group. A polymer chain-modified surface solid, wherein a polymer chain containing the base structural unit (B) is grafted via a polymerization initiation group introduced on the solid surface.

[4] The polymer chain obtained by chemically reacting a1 of the structural unit (A) with an organic group of b1 of the structural unit (B) using the grafted polymer chain of [3]. A polymer chain-modified surface solid characterized in that a network based on covalent bonds is formed between them.

[5] In the spreading range of the solid surface,
The polymerization initiation group introduced on the solid surface is formed in a pattern preliminarily divided into a polymerization initiation group that retains the activity and a polymerization initiation group that is inactivated, and the polymerization initiation group that retains the activity is highly classified. The polymer chain-modified surface solid according to any one of [1] to [4] above, wherein the molecular chain is grafted.

[6] The polymer chain-modified surface solid according to any one of the above [1] to [5], wherein the grafting of the polymer chain is based on living radical polymerization.

[7] Step I: Step of introducing a polymerization initiation group into the solid surface, Step II: The following formula (1) using the introduction group obtained in the above step as a starting source

[0018]

[Chemical 10]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
In the organic functional group of 8, R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. ) A step of homopolymerizing the α, β-unsaturated monomer (a) having an organic group on the side chain and grafting on the solid surface, or the α, β-unsaturated monomer (a) And a monomer (b) which is copolymerized with the above-mentioned monomer
Radical copolymerization with and grafting to the solid surface,
A method for producing a polymer chain-modified surface solid, which comprises sequentially performing

[8] The method for producing a polymer chain-modified surface solid according to [2] above, further comprising the step II of the polymer chain-modified surface solid obtained by the above-mentioned production method [7].
I: a step of converting a part or all of the organic groups of the polymer side chain into a carboxyl group or a carboxyl group by a hydrolysis reaction or a heating reaction, and a method for producing a polymer chain-modified surface solid.

[0021]

[9] Step I: Step of introducing polymerization initiation group into solid surface, Step II; Formula (1) below using the introduction group obtained in the above step as a starting source

[0022]

[Chemical 11]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
In the organic functional group of 8, R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. ), Α, β-unsaturated monomer having an organic group on the side chain and α, β-unsaturated monomer having an organic group that reacts with a carboxyl group are radically copolymerized to form a solid surface. A method for producing a polymer chain-modified surface solid, which comprises sequentially performing a step of grafting.

[10] Step I: a step of introducing a polymerization initiation group into the solid surface, Step II; the following formula (1) using the polymerization initiation group obtained in the above step as an initiation source:

[0025]

[Chemical 12]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
In the organic functional group of 8, R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. ) Organic group (a1)
Solid-state by radical-copolymerizing an α, β-unsaturated monomer (a) having a side chain with an α, β-unsaturated monomer (b) having an organic group (b1) that reacts with a carboxyl group. A step of grafting to the surface, a step III: a step of forming a network based on a covalent bond between the polymer chains by subsequently performing a chemical reaction between the organic group (a1) and (b1), A method for producing a polymer chain-modified surface solid, which is characterized.

[11] The above-mentioned [7] to [10], wherein the polymerization initiation group has a living radical polymerization initiating ability, and the polymerization is living radical polymerization or living radical copolymerization. Method for producing polymer chain-modified surface solid.

[12] In the method for producing a polymer chain-modified surface solid according to any one of [7] to [11], a step (I) of chemically bonding a polymerization initiation group to the surface of the solid
And during the subsequent grafting step (II), a step A; a step of inactivating the polymerization initiating group in a region divided in a predetermined pattern by electron beam or light irradiation, Next, a method for producing a polymer chain-modified surface solid, which comprises performing a graft polymerization step in the activated region.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The polymer chain-modified surface solid of the present invention has a side chain of the following formula (1)

[0030]

[Chemical 13]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
In the organic functional group of 8, R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. ) Organic group (a1)
And a polymer chain containing a structural unit based on the α, β-unsaturated monomer (a) having a group is grafted via a polymerization initiation group introduced on the solid surface. .

The solid to be grafted onto the surface of the polymer chain used in the present invention is not particularly limited, and organic materials,
It can be appropriately selected regardless of whether it is an inorganic material or a metal material. When imparting hydrophilicity to the surface, which is one of the objects of the present invention, there is a strong demand for the surface of biomaterials, transparent plastic films, transparent glass, etc. In this case, polyurethane-based materials, polyvinyl chloride-based materials , Polystyrene film, polyolefin film, polycarbonate film, P
MMA film, PET film, cellulose acetate film and silica inorganic glass are preferably selected.
In addition, when imparting hydrophilic / hydrophobic separation sites to the surface, it is required on the surface of printing materials, etc.
Examples include paper / plastic laminated films, metal plates and foils (aluminum, zinc, copper, etc.), paper on which metal is vapor deposited, and the like. Further, when imparting resistance to wet etching, alkali etching, chemical dry etching, plasma dry etching, etc. to the surface, it is an essential property for materials that require various patterning regardless of conductor, semiconductor, or insulator. Silicon wafers, silicon oxide films, silicon nitride, polycrystalline silicon and the like can be mentioned as the frequently used solids. Among these solids, a polycarbonate film, a PMMA film, a PET film, a metal plate of aluminum or copper, a metal plate, a silicon substrate, or the like is more preferable from the viewpoint of availability and versatility.

The polymer chain-modified surface solid of the present invention has a polymerization initiation group physically and chemically bonded to the surface of the solid, and more preferably a polymerization initiation group chemically bonded to the solid surface. The polymer chain is grafted via the initiating group. There are no particular restrictions on the type of polymerization initiation group and the method of introduction, but it is possible to graft the polymer chains with primary control at high density, polymerization initiation groups that retain activity by light and electron beams, and deactivated polymerization initiation groups. From the viewpoint of ease of patterning into a living radical, a living radical polymerization initiation group capable of promoting atom transfer radical polymerization, such as a halogenated alkyl group and a sulfonyl halide group, is particularly preferably adopted. Such an initiation group can be introduced according to the method described in JP-A No. 11-263819. That is, in short, a compound having a functional group capable of chemically bonding to a solid surface and a halogenated alkyl group or a halogensulfonyl group is used, and a reaction is introduced on the solid surface to introduce a polymerization initiation group. Taking a silicon substrate as an example,
A chlorosulfonyl group capable of initiating living radical polymerization by reacting 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane, 2- (4-chlorosulfonylphenyl) ethyltrichlorosilane, or the like with the oxide layer on the surface of the silicon substrate. It is possible to chemically bond and immobilize on the surface of a silicon substrate.

The high degree of hydrophilicity is achieved by controlling the primary structure of the polymer chains expressing hydrophilicity and grafting at a high density. As a method of introducing such a polymer chain,
A living radical polymerization method is particularly effective, in which the growth of all graft chains proceeds almost uniformly and steric hindrance between adjacent graft chains can be reduced. Α of the component (a) used in the present invention,
The β-unsaturated monomer has a side chain of the following formula (1)

[0035]

[Chemical 14]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
In the organic functional group of 8, R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. ) An organic group (hereinafter,
Sometimes called a hemiacetal ester bond. Is an α, β-unsaturated monomer (a). The above-mentioned monomer of the component a can smoothly undergo living radical polymerization through the polymerization initiation group introduced on the solid surface to graft a high-density polymer chain, and further, the side chain of the grafted polymer. Can be easily converted to a carboxyl group or a carboxyl group to specifically express high hydrophilicity.

The α, β-unsaturated monomer (a) having a hemiacetal ester bond in the present invention contains a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid or fumaric acid. an α, β-unsaturated monomer and the formula (2)

[0038]

[Chemical 15]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
8 an organic group, R ³ and R ⁴ may form a heterocyclic structure which comprises Y with heteroatoms bonded with each other, Y is an oxygen atom or a sulfur atom. ) A vinyl ether compound represented by the formula (1), a vinyl ether thioether compound or a cyclic vinyl ether compound such as a heterocyclic compound having a vinyl type double bond having an oxygen atom or a sulfur atom as a hetero atom, in the presence of an acid catalyst, preferably at room temperature. Or 2
It can be easily synthesized by adding at a temperature of 00 ° C.

Specific examples of the above-mentioned compounds include:
1-methoxyethyl acrylate, 1-ethoxyethyl acrylate, 1-n-propoxyethyl acrylate, 1-iso-propoxyethyl acrylate, 1-
n-Butoxyethyl acrylate, 1-iso-butoxyethyl acrylate, 1- (2-ethylhexoxy)
Ethyl acrylate, pyranyl acrylate, 1-methoxyethyl methacrylate, 1-ethoxyethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-i
so-propoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-iso-butoxyethyl methacrylate, 1- (2-ethylhexoxy) ethyl methacrylate, pyranyl methacrylate, di-1-methoxyethyl malate, di -1-ethoxyethylmalate, di-1-n-propoxyethylmalate, di-1-iso
-Propoxyethyl malate, di-1-n-butoxyethyl maleate, di-1-iso-butoxyethyl maleate, dipyranyl malate and the like can be mentioned.

Among these, 1-n-propoxyethyl acrylate, 1-iso-propoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-i
so-butoxyethyl acrylate, 1-n-propoxyethyl methacrylate, 1-iso-propoxyethyl methacrylate, 1-n-butoxyethyl methacrylate,
1-iso-butoxyethyl methacrylate has a living radical polymerizability and is easily converted into a carboxyl group,
It is particularly preferably selected.

The α, β-unsaturated monomer having a specific structure in the present invention may be polymerized alone or may be copolymerized with another α, β-unsaturated monomer having copolymerizability. As a living radical polymerization method for grafting, Macromolec
It is preferable to employ the atom transfer radical polymerization method described in ules, 1998, vol. 31, p. 5934-5936. Graft polymerization can be carried out by immersing the solid in a polymerization medium, or by coating the surface of the solid with the polymerization medium, employing the conditions described in the above-mentioned literature, and performing predetermined heating. Grafting reaction based on atom transfer radical polymerization is
As described in the above-mentioned documents and the like, it is reversible by withdrawing the polymer terminal halogen introduced via the polymerization initiation group on the solid surface with the redox reaction of a transition metal such as copper bromide. Monomers are added to the polymer growth radicals that are generated, and proceed. In this grafting reaction,
For example, allowing a living radical polymerization initiator such as ethyl 2-bromoisobutyrate to exist in the polymerization medium in a free state is also an effective method from the viewpoint of controlling the structure of the graft chain and can be preferably used.

The side chain of the polymer grafted on the solid surface in the present invention is easily converted into a carboxyl group or a carboxyl group by a hydrolysis reaction or a heating reaction due to the specificity of the structure (hemiacetal ester bond). Can be made. In the case of the heating reaction, the polymer chain-modified solid is preferably left in an atmosphere at 100 ° C. or higher to be converted into a carboxyl group with elimination of vinyl ether. Further, by using a laser or the like such that the irradiation site has a high temperature of 100 ° C. or more, it is possible to make only a specific irradiation site hydrophilic in the surface solid, and the hydrophilic site and the hydrophobic site are desired positions. Surface solids present in the can be obtained. On the other hand, when the polymer chain-modified solid is immersed in water, acidic or alkaline water,
Hydrolysis of the hemiacetal ester bond in the side chain of the polymer is promoted, and it can be converted into a carboxyl group or a carboxyl group. By these reactions, a surface solid having extremely high hydrophilicity is obtained, and since the polymer chains are firmly bound to the solid surface, the hydrophilicity is permanently maintained.

Further, the surface solid having etching resistance and the like is a specific α, β-unsaturated monomer (a) having a hemiacetal ester bond via the polymerization initiation group on the solid surface.
And an α, β-unsaturated monomer (b) having an organic group (b1) that reacts with a carboxyl group are copolymerized by a living radical polymerization method to form an α, β- having a hemiacetal ester bond in a side chain. A high content containing a structural unit (A) based on an unsaturated monomer (a) and a structural unit (B) based on an α, β-unsaturated monomer (b) having an organic group that reacts with a carboxyl group. It can be obtained by grafting a molecular chain and then chemically reacting the organic groups of the structural unit (A) and the structural unit (B) to form a network based on covalent bonds between the polymeric chains. Further, in the polymerization for forming the structural unit (A) and the structural unit (B), α, β-of the third component which is copolymerizable with the α, β-unsaturated monomer constituting these units. The unsaturated monomer (c) can also be copolymerized and used.

The α, β-unsaturated monomer (b) having an organic group which reacts with a carboxyl group includes an epoxy group, a silanol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group and an isocyanate in the side chain. Examples of the unsaturated monomer include a group, a blocked isocyanate group, a cyclocarbonate group, a vinyl ether group, a vinyl thioether group, an aminomethylol group, an alkylated aminomethylol group, an acetal group, and a ketal group. Specifically, α, β-unsaturated epoxy compounds such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate; acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, methacryloyloxy. Propyltri-n-butoxysilane and other α, β-unsaturated silane compounds and silanol group- and alkoxysilane group-containing compounds that are hydrolyzed compounds of these compounds; 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) ) Α, β-Unsaturated compounds such as acrylates and hydroxyl group-containing compounds such as ε-caprolactone adducts thereof; 3- (meth) acryloyloxypropylene carbonate, vinyloxyalkyl (meth) acrylates, aminomethyi Lumpur group or alkylated aminomethylol group-containing alpha, a β- unsaturated compounds. Among them, glycidyl (meth) acrylate, acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxy, from the viewpoints of availability, living radical copolymerizability, easiness of reaction with carboxyl group, and network formation having etching resistance. Silane and methacryloyloxypropyltri-n-butoxysilane are preferred, and glycidyl (meth) acrylate is particularly preferred.

The organic group (a1) represented by the above formula (1) contained in the structural unit (A) in the polymer chain of the present invention regenerates a free carboxyl group under heating to generate the structural unit (B). In order to easily form a chemical bond with the organic group (b1) which reacts with the carboxyl group in (1), a heat treatment at 100 ° C. or higher, preferably 120 ° C. or higher may form a network between polymer chains. it can. The ratio of the structural unit (A) to the structural unit (B) in the polymer chain is not particularly limited,
In order to form a strong mesh, the organic group (a) in the structural unit (A) is
1) / the molar equivalent ratio of the organic group (b1) of the structural unit (B) is preferably 0.2 / 1.0 to 1.2 / 1.0, and the molar equivalent ratio is 0. .5 / 1.0 to 1.1 / 1.
When it is 0, a stronger mesh is formed. Further, the ratio of both α, β-unsaturated monomers when performing living radical polymerization is preferably set similarly.

In order to form a pre-divided pattern of the polymerization initiation group which retains the activity and the polymerization initiation group which is inactivated as proposed in the present invention, the polymerization of a halogenated alkyl group or a sulfonyl halide group is initiated. A method of decomposing the polymerization initiation group by irradiating the solid surface bonded as a group with active energy such as ultraviolet rays (using a high pressure mercury lamp) or an electron beam in a predetermined pattern is used. By appropriately selecting an irradiation source and a mask, performing irradiation using, for example, an electron beam mask drawing device to form a fine pattern of inactive sites and active sites, and then performing a grafting reaction by living radical polymerization. , Graft modification in fine patterned areas can be achieved.

Surface modification in which the constituent unit based on the α, β-unsaturated monomer (a) having the organic group (a1) represented by the formula (1) is grafted and introduced on the surface thus obtained. The solid can be easily converted to a carboxyl group or a carboxyl base by hydrolysis by heating or the like. Therefore, the polymer chain-modified surface solid can be converted into a carboxyl group or the like to become a hydrophilic solid surface. In the method for producing the modified surface solid of the present invention, since the α, β-unsaturated monomer (a) having the hemiacetal group represented by the formula (1) in the side chain is used, the grafting reaction can be controlled. It will be easier. For example, [i] In the case of converting to a carboxyl group as described above, the reactivity can be remarkably improved as compared with the case of directly grafting a monomer having a carboxyl group. In the case of copolymerizing with another monomer, the compatibility of the monomer composition and the copolymerizability are expected to improve. [Ii] Further, by using the above-mentioned monomer (a), it can be easily converted into hydrophilic. For example, by irradiating the irradiation site with energy rays that are exposed to high temperatures, the vinyl ether group can be locally eliminated to make it hydrophilic, so that the solid surface is provided with hydrophilic and oily parts. By using such a substrate, it can be used as a substrate for printing or the like. [Iii] Furthermore, a monomer (a) having a hemiacetal group represented by the above formula (1) and a monomer (b) having an organic group (b1) that reacts with a carboxyl group are grafted onto a solid surface. When copolymerized, the graft chain of A and B
It can be cross-linked with the graft chain of, and a stronger graft chain can be obtained. In addition, the polymerization initiation group introduced on the surface of the solid is irradiated with energy rays in advance by using a mask or the like to divide the active portion and the inactive portion, whereby a fine pattern can be formed. Can be grafted to. At that time, crosslinking by heating or the like can exert excellent effects such as etching resistance, so that it can be suitably used as a substitute material for a photoresist substrate or the like. Therefore, the surface-modified solid obtained by these methods is industrially useful for various applications.

[0049]

The present invention will be described in more detail based on the following examples. Example 1 <Introduction of living radical polymerization initiation group to solid surface> 2
-(4-chlorosulfonylphenyl) ethyltrichlorosilane (CTS) in 0.1% dehydrated toluene solution (0.1
% Of methylene chloride), the silicon substrate subjected to the ion sputtering treatment for 5 minutes was immersed at 25 ° C. for 24 hours. Toluene, then TH
It was thoroughly washed with F (tetrahydrofuran) and then dried to obtain a silicon substrate having a chlorosulfonyl group fixed on the surface. <Surface graft polymerization> 1-n-propoxyethyl methacrylate (n-PEMA) 150 parts, anisole 150
And 0.1 parts of ethyl 2-bromoisobutyrate were added to a mixed solution so that the concentration of copper bromide was 10.5 mM to prepare a polymerization solution. The above substrate is immersed in this, and after degassing and sealing, 50
Graft polymerization was carried out by heating to ° C. The molecular weight and molecular weight distribution of the free polymer formed in the solution were determined by GPC, and the film thickness of the polymer chains grafted on the substrate was determined by ellipsometry after thoroughly washing with chloroform. Although it is difficult to directly measure the molecular weight of the grafted polymer chain, it can be regarded as almost the same as the free polymer formed in the solution because of the mechanism of polymerization. The molecular weight of the free polymer and the dry film thickness of the graft film increased proportionally with the polymerization time. Graft density calculated from the relationship between molecular weight and graft thickness is 0.4
It was chains / nm ² . Further, the graft film thickness 7 hours after the initiation of polymerization was 40 nm, and the molecular weight of the graft polymer chain assumed from the molecular weight of the free polymer was 60,000. From this result, it became clear that a surface solid in which polymer chains were grafted at an extremely high density could be obtained.

Example 2 <Applying hydrophilicity by conversion into carboxyl group and carboxyl group> Silicon substrate obtained in Example 1 (polymer chain-modified surface solid)
Was left in an atmosphere of 180 ° C. for 1 hour. As a result of IR analysis of the surface before and after standing at 180 ° C., a peak derived from hemiacetal ester observed before standing (1720c
m ^-1 ) almost disappeared after standing at 180 ° C, and the acid form (171
It was confirmed to have changed to 0 cm ⁻¹ ). Further, the contact angle with water was measured, and it was shown that the hydrophilicity was improved up to 25 degrees after being left at 180 ° C., whereas it was 80 degrees before being left standing.

The silicon substrate obtained in Example 1 was adjusted to pH.
It was immersed in a 50 ° C. KOH aqueous solution adjusted to 12 for 5 hours. When IR analysis and contact angle measurement with respect to water were carried out on the substrate that had been thoroughly washed with water and dried, the peak (1720 cm ^-1 ) derived from the hemiacetal ester disappeared and 1550
It was confirmed that a new peak was generated at cm ^-1 .
Further, the contact angle was almost 0 degree, and it was found that a highly hydrophilic surface was formed.

The surface-grafted silicon substrate obtained in Example 1 was irradiated with laser light of 830 nm while forming a pattern (the laser stayed at one point:
220 μs, surface temperature of irradiation site: set conditions of about 150 ° C). When the substrate subjected to this treatment was dipped in a toluene solution in which a blue oily dye was dissolved, only the non-irradiated part was vividly colored blue. On the contrary, when it was immersed in an aqueous solution in which a red aqueous dye was dissolved, only the irradiated portion was colored red. From these results, it can be seen that the laser-irradiated portion is desorbed of the vinyl ether group to be hydrophilic to the carboxyl group, and the laser-irradiated portion is still hydrophobic. Therefore, it was suggested that the polymer chain-modified surface solid of the present invention is applicable to applications such as lithographic printing.

Comparative Example 1 <Surface Graft Polymerization> A silicon substrate in which a polymerization initiation group was not introduced was immersed in the polymerization solution prepared in Example 1, and living radical polymerization was carried out under the same conditions as in Example 1. As a result, although a free polymer was generated in the polymerization solution, a graft layer was not formed on the substrate surface, and a hydrophilic surface could not be obtained even by performing the same operation as in Example 2.

Examples 3 to 8 and Comparative Examples 2 to 4 100 parts of α, β-unsaturated monomer in the ratio shown in Table 1, 100 parts of anisole, ethyl 2-bromoisobutyrate 0.07
A polymerization solution was prepared by adding copper bromide to the mixed solution of 1 part so that the concentration thereof was 7 mM. A silicon substrate having a living radical heavy initiation group introduced therein prepared by the same method as in Example 1 was dipped in this solution, degassed and sealed and heated at 80 ° C. for graft polymerization. Molecular weight (value after 6 hours reaction), dry thickness of graft layer (value after 6 hours reaction), graft density (6
The method of measuring the value after the time reaction) is the same as in Example 1.
Further, the contact angle to water and the swollen film thickness of the graft layer are 1
The measurement was performed after heating at 80 ° C. for 2 hours to convert to a carboxyl group or carry out a reaction of carboxyl group / glycidyl group. The swollen film thickness is measured by an ellipsometry method by immersing the substrate in an aqueous NaOH solution having a pH of 11, and the thicker the film, the higher the hydrophilicity and the absorption of free water and the extension of the graft chain. Is shown. After the contact angle was measured, a rubbing test was repeated 100 times using a wipe whose surface was moistened with acetone. The measurement results are shown in Table 1.

[0055]

[Table 1]

The notes in the table are as follows. 1) Iso-PEMA: 1-iso-propoxyethyl methacrylate, GMA: glycidyl methacrylate, MMA: methyl methacrylate, MAA: methacrylic acid

In Examples 3 to 8 and Comparative Example 2, the grafting reaction proceeded smoothly. However, in Comparative Example 3 in which the polymerization was carried out without protecting the carboxyl group, the formation of a graft chain was not observed, and a gel-like precipitate was generated in the polymerization system. Further, in Comparative Example 4, the entire polymerization liquid was gelled 4 hours after the initiation of the polymerization, and the reaction could not be continued. On the other hand, in Examples 3 to 8, it was revealed that the same level of graft layer thickness and graft density as in Comparative Example 2 was achieved. From this result, it can be seen that the method of the present invention in which the carboxyl group is protected and subjected to the polymerization is effective in performing living radical polymerization. In addition, Examples 3 to 5,
From the comparison of the results of Comparative Example 2, it can be seen that the polymer chain-modified surface solid of the present invention also exhibits good hydrophilicity, shows no change in hydrophilicity after acetone rubbing, and is excellent in durability. From the results of the swollen film thickness measurements of Examples 6 to 8,
It can be seen that a layer which is not attacked by the alkaline aqueous solution is formed by the heat treatment after grafting. It was also suggested that it has excellent alkali etching resistance. In addition, it was found that the contact angle did not change even in the acetone rubbing test, and the solvent etching resistance was also excellent.

Examples 9 to 13 and Comparative Examples 5 and 6 JEOL Ltd. was used for a silicon substrate having a living radical polymerization initiation group introduced therein prepared in the same manner as in Example 1.
Using an electron beam mask drawing device (JBX-5000FS), 1.0 μm width (irradiation) /0.7 μm width (unirradiated) under the conditions of accelerating voltage: 20 kV, current: 20 pA, and electron beam irradiation amount: 2200 μC / cm 2. ) /0.5 μm width (irradiation)
A pattern of /0.3 μm width (unirradiated) /0.2 μm width (irradiated) was irradiated to form active sites (unirradiated) and inactive sites (irradiated) of the polymerization initiation group on the substrate surface.

Then, a mixed solution of 100 parts of α, β-unsaturated monomer, 100 parts of anisole and 0.07 part of ethyl 2-bromoisobutyrate in a ratio shown in Table 2 was used, and the copper bromide concentration was 7 m.
The above-mentioned substrate was immersed in a polymerization solution which was added and adjusted so as to have M, degassed and sealed, and subjected to a grafting reaction at 80 ° C. for 8 hours. After the polymerization, each substrate was thoroughly washed with chloroform and then heat-treated at 180 ° C. for 2 hours.
Then, wash thoroughly with chloroform again and
After drying for an hour, the following evaluation was performed.

Analysis by AFM (atomic force microscope)
The pattern formation state and the graft film thickness were evaluated. The pattern formation state was judged from the sharpness of the boundary between the electron beam-irradiated site and the unirradiated site. (∘: four boundary areas are sharp, ×: any one of the boundary areas lacks sharpness). Further, the thickness difference between the electron beam non-irradiated portion and the electron beam irradiated portion was defined as the graft thickness. For Examples 9 and 10 and Comparative Example 5, the substrate was immersed in an aqueous solution in which the red aqueous dye was dissolved in order to determine whether the graft site was clearly patterned and the hydrophilicity was developed. The substrate was observed with an optical microscope. (The evaluation is as follows.
◯: Hydrophilicity is retained and the dye is sufficiently adsorbed only by the graft site. ×: Hydrophilicity is not expressed and adsorption of the dye is not observed. )

The etching resistance of Examples 11 to 13 and Comparative Example 6 was evaluated. Etching resistance-1: 180
A silicon substrate heat-treated at 2 ° C. for 2 hours has a pH of 14 Na.
It was immersed in a strong OH aqueous solution at 50 ° C. for 2 hours. Then, after washing with water and drying, the shape was observed by SEM (scanning electron microscope). (Evaluation is as follows: ◯: No deformation of the graft layer site is observed, Δ: A decrease in the film of the graft layer site is observed, ×: The graft layer site is destroyed.)
Etching resistance-2: 180 ° C. A silicon substrate that had been heat treated for 2 hours was introduced into a vacuum chamber, and after being evacuated, an etching gas (CF ₄ ) was introduced, and the gas was converted into plasma for dry etching. The substrate taken out of the chamber was observed by SEM to evaluate the degree of progress of etching of the silicon oxide film site (corresponding to the electron beam irradiation site) and the graft layer site (corresponding to the electron beam non-irradiation site). (Evaluation is as follows: ◯: The silicon oxide film site is removed by etching, but the deformation of the graft layer site is retained. ×: Both the silicon oxide film site and the graft layer site are found to be removed. .)

Table 2 shows the evaluation results of the examples and comparative examples.

[0063]

[Table 2]

It can be seen that good pattern shapes were obtained in each of the examples and comparative examples. However, in Comparative Example 5, no expression is seen in the fine region of the hydrophilic component.
Further, in Comparative Example 6, etching resistance is not recognized.
On the other hand, in Examples 9 and 10 intended to form a fine pattern of the hydrophilic portion, it can be seen that the purpose is sufficiently achieved. Further, Examples 11 to 13 are intended to impart etching resistance in a fine region, but show good results in both dry etching and wet etching. Therefore, the present invention is applicable to semiconductor resists and various patterning. It is suggested that it is useful as a surface modification method for required materials.

[0065]

INDUSTRIAL APPLICABILITY The polymer chain-modified surface solid according to the present invention exhibits high hydrophilicity because polymer chains having a carboxyl group or a carboxyl group are grafted at a high density. Further, since it is modified with a polymer chain having a strong network structure, practical properties such as etching resistance can be imparted at a high level. Furthermore, according to the production method of the present invention, the living radical polymerization of the specific monomer used for the purpose of imparting these characteristics smoothly proceeds, and the polymer chain having a controlled primary structure becomes dense. A grafted surface solid is obtained.

Claims (12)

[Claims] 1. A side chain of the following formula (1): (In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic functional group having 1 to 18 carbon atoms, and R ³ and R ⁴ are bonded to each other. To form a heterocycle having Y as a hetero atom, Y is an oxygen atom or a sulfur atom, and α having an organic group (a1) represented by
Polymer chain modification characterized in that a polymer chain containing a structural unit based on the β-unsaturated monomer (a) is grafted via a polymerization initiation group introduced on the solid surface. Surface solid. 2. The side chain in the polymer chain according to claim 1, represented by the following formula (1): (In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic functional group having 1 to 18 carbon atoms, and R ³ and R ⁴ are bonded to each other. To form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom.) A part or all of the organic group represented by A polymer chain-modified surface solid characterized by being converted into a carboxyl base. 3. A side chain having the following formula (1): (In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic functional group having 1 to 18 carbon atoms, and R ³ and R ⁴ are bonded to each other. To form a heterocycle having Y as a hetero atom, Y is an oxygen atom or a sulfur atom, and α having an organic group (a1) represented by
Structural unit (A) based on β-unsaturated monomer (a), and structural unit (B) based on α, β-unsaturated monomer (b) having an organic group (b1) that reacts with a carboxyl group A polymer chain-modified surface solid comprising a polymer chain containing and, which is grafted through a polymerization initiation group introduced on the solid surface. 4. A high molecular weight compound obtained by chemically reacting the organic group a1 of the structural unit (A) with the organic group b1 of the structural unit (B) using the grafted polymer chain according to claim 3. A polymer chain-modified surface solid characterized in that a network based on covalent bonds is formed between the molecular chains. 5. The polymerization initiation group introduced into the solid surface in a spread range of the solid surface is formed in a pattern preliminarily divided into a polymerization initiation group which retains activity and a polymerization initiation group which is inactivated, and The polymer chain-modified surface solid according to any one of claims 1 to 4, wherein a polymer chain is grafted to a section of the polymerization initiation group that retains the activity of. 6. The grafting of the polymer chain is based on living radical polymerization.
5. The polymer chain-modified surface solid according to any one of 5 above. 7. Step I: a step of introducing a polymerization initiation group onto the surface of a solid, Step II: using the introduction group obtained in the above step as a starting source, the following formula (1): (In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic functional group having 1 to 18 carbon atoms, and R ³ and R ⁴ are bonded to each other. To form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom.) An α, β-unsaturated monomer having an organic group (a1) represented by a side chain. A step of homopolymerizing (a) and grafting on a solid surface, or a monomer (c) copolymerizable with the α, β-unsaturated monomer (a) and the monomer of a. A method for producing a polymer chain-modified surface solid, which comprises sequentially performing a step of radically copolymerizing the above with a solid surface. 8. The method for producing a polymer chain-modified surface solid according to claim 2, further comprising the polymer chain-modified surface solid obtained by the production method according to claim 7, further comprising Step III: hydrolysis reaction or A method for producing a polymer chain-modified surface solid, comprising the step of converting a part or all of the organic groups on the polymer side chain into a carboxyl group or a carboxyl group by a heating reaction. 9. Step I: a step of introducing a polymerization initiation group into the solid surface, step II; using the introduction group obtained in the above step as a starting source, the following formula (1): (In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic functional group having 1 to 18 carbon atoms, and R ³ and R ⁴ are bonded to each other. To form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom.) An α, β-unsaturated monomer having an organic group (a1) represented by a side chain. The step of performing radical copolymerization of (a) and an α, β-unsaturated monomer (b) having an organic group (b1) that reacts with a carboxyl group and grafting it onto a solid surface is sequentially performed. And a method for producing a polymer chain-modified surface solid. 10. Step I: a step of introducing a polymerization initiation group into the solid surface, step II; using the polymerization initiation group obtained in the above step as an initiation source, the following formula (1): (In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic functional group having 1 to 18 carbon atoms, and R ³ and R ⁴ are bonded to each other. To form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom.) An α, β-unsaturated monomer having an organic group (a1) represented by a side chain. A step of radically copolymerizing (a) and an α, β-unsaturated monomer (b) having an organic group (b1) that reacts with a carboxyl group and grafting it onto a solid surface, Step III: then an organic group ( A method for producing a polymer chain-modified surface solid, which comprises sequentially performing a step of chemically reacting a1) and (b1) to form a network based on covalent bonds between polymer chains. 11. The polymerization initiation group has a living radical polymerization initiation ability, and the polymerization is living radical polymerization or living radical copolymerization.
0. The method for producing a polymer chain-modified surface solid according to any one of 0. 12. The method for producing a polymer chain-modified surface solid according to any one of claims 7 to 11, wherein the step (I) of chemically bonding a polymerization initiation group to the surface of the solid and the subsequent grafting. During the step (II), a step A; a step of inactivating the polymerization initiation group in the region divided in a predetermined pattern by electron beam or light irradiation, and then the activated A method for producing a polymer chain-modified surface solid, which comprises performing a graft polymerization step in a region.