JP7099328B2 - Wiring formation method - Google Patents

Description

The present invention relates to a wiring forming method using a catalyst ink for forming an undercoat layer of electrolytic metal plating. Specifically, the present invention applies a catalyst ink to a film having a parent liquid portion and a liquid repellent portion, and a plating solution. The present invention relates to a wiring forming method by contacting with and precipitating plating.

Conventionally, in the manufacture of circuits, sensors, elements and the like, methods such as a pattern forming technique using a resist, a sputtering technique, and a plating technique by a vacuum vapor deposition method have been used. However, these methods have the disadvantages that a step of removing unnecessary parts by etching is required and that a large amount of energy is consumed by making full use of vacuum and high temperature. Therefore, in recent years, printed electronics applying printing technology have been attracting attention from the viewpoint of process simplicity and economy. The inkjet method is a typical example of such a printing technique. This is a printing technology that applies the required amount of material only to the required parts, and since it does not require a vacuum process, it is expected to lead to significant resource and energy savings when applied to the electronics manufacturing field. There is. As an electronic material using such an inkjet method, an ink for forming a conductor pattern has been proposed so far (Patent Document 1).
In addition, in the manufacture of circuits, sensors, elements, etc., there is a global need for the development of manufacturing technology that can be made highly functional, compact and lightweight, in order to achieve mobile and high functionality of information and communication equipment. For example, in wiring technology, further thinning of metal patterns is required.

On the other hand, in electroless plating, a metal film having a uniform thickness can be obtained by simply immersing the base material in a plating solution under mild conditions, regardless of the type and shape of the base material. A general plating process includes a pretreatment step of a base material such as degreasing and etching, a catalyst step of adsorbing a catalyst, an accelerator step of activating the catalyst, and a step of immersing in an electrolytic plating solution.
A method of forming a metal pattern by utilizing such electroless plating technology has also been proposed. For example, a catalyst ink containing a palladium metal salt and a complexing agent is formed into a pattern by inkjet, and a metal is formed by electroless plating. A method for causing the plating is disclosed (see Patent Document 2). However, in this method, a step for reducing and activating Pd ions (the accelerator step) is indispensable, and the operation is complicated.

On the other hand, it is known that electrodes, wiring, etc. are formed by irradiating a coating film whose lipophilicity and liquid repellency change with light in a pattern and then applying metal ink to the parental liquid portion. (For example, Patent Document 3). However, the formation of electrodes and wiring with metal ink requires a sintering process in order to reduce the resistance value, which is generally performed at a high temperature of over 150 ° C. Therefore, it is possible to form wiring or the like on a film substrate or the like. could not.
In addition, there is an example in which the catalyst ink for electroless plating is applied on a pattern having a parent liquid part and a liquid repellent part, but it is applied to the entire surface of the substrate, and an ink that stably ejects by inkjet has been studied. Not available (Patent Document 4).

Japanese Unexamined Patent Publication No. 2012-12239 International Publication No. 2010/067696 Pamphlet Patent No. 4743254 Japanese Unexamined Patent Publication No. 2016-157111

As described above, in recent years, further thinning of the metal pattern has been required. However, when a pattern of 100 μm or less is formed by the inkjet method, the droplets become smaller, which causes disconnection and stable ink ejection. There is a problem that the printing speed becomes slow. However, it is desired to apply it by inkjet in order to improve the efficiency of using the material.
Therefore, the present invention pays attention to such a problem, and a catalyst is obtained on a coating film having a parent liquid portion and a liquid repellent portion, in which a fine wire pattern having no disconnection and excellent straightness, for example, a fine wire pattern of 50 μm or less can be obtained by electroless plating. It is an object of the present invention to provide a new wiring forming method by applying ink by inkjet. In the present specification, "straightness" means a property that the line width can always be kept constant in the length direction of a thin line.

As a result of diligent studies to achieve the above object, the present inventors have an ammonium group at the molecular end as a catalyst ink for electroless plating and have a weight average molecular weight of 1,000 to 5,000,000. By adopting a method of applying a catalytic ink composed of a hyperbranched polymer and metal fine particles on a film having a parent liquid portion and a liquid repellent portion, pattern formation with a line width of 50 μm or less can be achieved, and such. The present invention has been completed by finding that the thin line pattern does not cause disconnection, the line width is constant, and the pattern has excellent straightness.

（式中、Ｒ^１１は水素またはメチル基を表し、Ｒ^１２はそれが結合する酸素原子を伴って脱離可能な有機基を表す。）
第８観点として、
親液部と撥液部とを有する膜が、さらに（Ｃ）成分として微粒子を含有する光親撥液部形成組成物により形成されたものである第７観点記載の配線形成方法。
第９観点として、
親液部と撥液部とを有する膜が、触媒インクに対する接触角が、撥液部では３０°以上であり、親液部では５°以下であるパターン形成膜である第４観点乃至第８観点のいずれか一向に記載の配線形成方法、
第１０観点として、
第１観点乃至第９観点のいずれかに記載の配線形成方法を用いて配線を形成してなる基材、
第１１観点として、
第１０観点に記載の基材を具備する装置に関する。That is, the present invention, as a first aspect,
Wiring formation method including the following steps A and B,
Step A: A step of providing a base layer by applying a catalyst ink on a base material having a parent liquid portion and a liquid repellent portion.
Step B: A step of immersing a base material provided with a base layer in an electroless plating bath to form a metal plating film.
As a second point of view
The catalyst ink is (a) dispersant,
(B) Metal fine particles,
(C) Wiring Forming Method Containing Solvent The wiring forming method according to the first aspect, which is an ink.
As a third point of view
A hyperbranched polymer in which the catalytic ink has (a) an ammonium group at the molecular end and a weight average molecular weight of 1,000-5,000,000.
(B) Metal fine particles,
(C) Wiring forming method containing a solvent The wiring forming method according to the first aspect, which is an ink.
As a fourth point of view
The first viewpoint, the second viewpoint, or the third viewpoint, in which the base material having the parent liquid portion and the liquid repellent portion is a base material formed by forming a film having the parent liquid portion and the liquid repellent portion on the base material. The wiring forming method described.
As a fifth point of view
The film having a liquid-repellent portion and a liquid-repellent portion has a liquid-repellent portion having a liquid-repellent group and a parent-liquid portion that is made liquid-repellent by desorption or decomposition of the liquid-repellent group by exposure. The wiring forming method according to a fourth aspect, which is characterized by being a film.
As a sixth point of view
The membrane having the parent liquid portion and the liquid-repellent portion is made liquid-friendly by the desorption of the liquid-repellent group by the action of the liquid-repellent portion having the liquid-repellent group and the acid generated by the exposure. The wiring forming method according to a fourth aspect, characterized in that it is a film having a portion.
As a seventh point of view
The membrane having the parent liquid part and the liquid repellent part,
It is formed by a polymer containing a structural unit derived from a monomer having the structure of the following formula (1) as a component (A), a photoacid generator as a component (B), and a photoparent liquid repellent portion forming composition containing a solvent. The wiring forming method according to any one of the fourth aspect to the sixth aspect.

(In the formula, R ¹¹ represents a hydrogen or methyl group and R ¹² represents an organic group that can be desorbed with an oxygen atom to which it is attached.)
As the eighth viewpoint
The wiring forming method according to the seventh aspect, wherein the film having the parent liquid portion and the liquid repellent portion is formed by a photoparent liquid repellent portion forming composition further containing fine particles as the component (C).
As a ninth point of view
The fourth to eighth viewpoints that the film having the parent liquid portion and the liquid repellent portion is a pattern forming film in which the contact angle with respect to the catalyst ink is 30 ° or more in the liquid repellent portion and 5 ° or less in the water repellent portion. The wiring forming method described in any one of the viewpoints,
As a tenth point of view
A substrate obtained by forming wiring using the wiring forming method according to any one of the first aspect to the ninth aspect.
As the eleventh viewpoint
The present invention relates to an apparatus provided with the substrate according to the tenth aspect.

In the wiring forming method of the present invention, a base layer of electroless metal plating having excellent linearity can be formed on a base material by using a catalyst ink.
The wiring forming method of the present invention can draw a fine line pattern of 50 μm or less, and can form a fine line pattern having a constant line width and excellent straightness without causing disconnection in the obtained fine line pattern.
Further, the base layer of the electrolyzed metal plating formed from the catalyst ink of the present invention can easily form a metal plating film on the base material simply by immersing it in the electrolyzed plating bath, and is metal-plated. A metal-coated substrate can be easily obtained.
That is, by forming a pattern on the substrate using the catalyst ink of the present invention and performing electroless plating, a metal plating pattern having a line width of 50 μm or less, suppressing the occurrence of disconnection, and having excellent straightness can be obtained. It can be formed, and this pattern forming technique is very useful in wiring techniques that require thinning.

The wiring forming method of the present invention is a wiring forming method including the following steps A and B.
Step A: A step of providing a base layer by applying a catalyst ink on a base material having a parent liquid portion and a liquid repellent portion.
Step B: A step of immersing a base material provided with a base layer in an electroless plating bath to form a metal plating film.
Hereinafter, the present invention will be described in detail.

[Base material having a parent liquid part and a liquid repellent part]
In order to prepare a base material having a parent liquid portion and a liquid repellent portion used in the present invention, a method of directly treating the surface of the base material and a coating film having the parent liquid portion and the liquid repellent portion are applied to the surface of the base material. The method of forming is mentioned.
Among these, as a method of directly treating the surface of the substrate, for example, a method of directly modifying the surface of the substrate by using vacuum ultraviolet light as described in WO2016 / 056232 can be mentioned.

When forming a film having a parent liquid portion and a liquid repellent portion, a cured film forming composition capable of giving a coating film whose lipophilicity and liquid repellent property are changed by light irradiation (hereinafter referred to as a photoparent liquid repellent portion forming composition). () Is applied onto a substrate, dried, and then irradiated with light in a pattern to form the film.

The film having such a liquid-repellent portion and the liquid-repellent portion is preferably formed by using a film that becomes lipophilic by desorbing or decomposing the liquid-repellent group in the exposed portion, and an acid in the exposed portion. It is more preferable to form a film using a membrane that becomes pro-liquid due to the desorption of the liquid-repellent group by the action of.

As the photoparent liquid-repellent portion forming composition, for example, a resin having a liquid-repellent group that can be desorbed by an acid and a composition in which a photoacid generator is dissolved in a solvent are preferably used.

Examples of such an acid dissociable group include acetal bonds, hemiacetal ester bonds, alkoxymethylol bonds and the like.
Examples of the liquid-repellent group include a fluorinated alkyl group and the like.

（式中、Ｒ^１１は水素またはメチル基を表し、Ｒ^１２はそれが結合する酸素原子を伴って脱離可能な有機基を表す。）Specifically, as shown below, a polymer containing a structural unit derived from a monomer having the structure of the following formula (1) as a component (A), a photoacid generator as a component (B), and a photorepellent containing a solvent. A liquid part-forming composition is preferable.

(In the formula, R ¹¹ represents a hydrogen or methyl group and R ¹² represents an organic group that can be desorbed with an oxygen atom to which it is attached.)

In addition to the component (A), the component (B), the component (C) and the solvent, the photoparent liquid-repellent portion forming composition further comprises other polymers other than the component (A) as the component (D), (E). ) A cross-linking agent can be contained as a component. Furthermore, other additives can be contained as long as the effects of the present invention are not impaired.
The present invention will be described with reference to the following items.

<Ingredient (A)>
The component (A) contained in the photoparent liquid-repellent portion forming composition used in the present invention is a polymer containing a structural unit derived from a first monomer having the structure of the above formula (1).
The component (A) is a polymer containing at least a structural unit derived from a monomer having the structure of the above formula (1) (in the formula, R ¹¹ and R ¹² are as defined above).

As the polymer of the component (A), in addition to the monomer having the structure of the above formula (1), a monomer having an unsaturated double bond such as an acrylic acid ester, a methacrylic acid ester, styrene, or a derivative thereof is used. Also included is a polymer obtained by subjecting to copolymerization.

Therefore, the component (A) includes
(A) A homopolymer of a kind of monomer having the structure of the above formula (1),
(B) A copolymer of two or more types of monomers having the structure of the above formula (1),
(C) A copolymer of a monomer having the structure of the above formula (1) and a monomer having an unsaturated double bond such as an acrylic acid ester, a methacrylic acid ester, styrene, or a derivative thereof. Be included.
The polymer of the component (A) (hereinafter, also referred to as a specific copolymer) may be a polymer having such a structure, and the skeleton of the main chain and the type of side chains of the polymer constituting the polymer may be used. Not particularly limited.

The polymer of the component (A) preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 2,000 to 150,000, and more preferably 3,000 to 100,000. Is even more preferable. If the weight average molecular weight is more than 200,000 and is excessive, the solubility in a solvent may be lowered and the handleability may be lowered, and if the weight average molecular weight is less than 1,000 and too small, it is cured. It may become insufficient and the solvent resistance and heat resistance may decrease. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample. Hereinafter, the same shall apply in this specification.

R ¹² in formula (1) represents an organic group that can be desorbed with an oxygen atom to which it is attached.
Preferably, R ¹² represents a hydrocarbon group or a fluorine-substituted hydrocarbon group (also referred to herein as a fluorine-substituted hydrocarbon group).
The hydrocarbon group which may be substituted with the fluorine may be branched and / or cyclized. Further, the hydrocarbon group may be interrupted by an aromatic ring, -O-, -S-, -CO-, -CS-, -NH-, or a combination thereof. Examples of such interrupting groups include, but are not limited to, phenylene, naphthylene, biphenylene, ether, thioether, carbonyl, carboxyl, amide, urea and the like.
The number of carbon atoms of R ¹² is preferably 2 or more, more preferably 2 to 18, and most preferably 2 to 10.

When R ¹² in the formula (1) is a hydrocarbon group, one of the typical R ¹² is an alkyl group.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and 1-methyl-n. -Butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl- n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl- n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2 , 3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl Group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl- n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl -N-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2- Ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl- n-Butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group, 2-methyl-n -Heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2- Dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl -N-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group, 2-methy Examples thereof include ru-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group and the like. ..

Specific examples of such a monomer include hydroxymethyl groups such as N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. Alternatively, an acrylamide compound or a methacrylamide compound substituted with an alkoxymethyl group can be mentioned. Note that (meth) acrylamide means both methacrylamide and acrylamide.

When R ¹² in the formula (1) is a hydrocarbon group substituted with fluorine, one of the typical R ¹² is a fluoroalkyl group.
The number of carbon atoms of the fluoroalkyl group is preferably 2 or more, 2 to 50, 2 to 30, 2 to 18, 2 to 10, 4 to 10, 4 to 8 in that order. These may be branched and / or cyclized.
Examples of such fluoroalkyl groups include 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, and 3-perfluorobutyl group. -2-Hydroxypropyl group, 2- (perfluorohexyl) ethyl group, 3-perfluorohexyl-2-hydroxypropyl group, 2- (perfluorooctyl) ethyl group, 3-perfluorooctyl-2-hydroxypropyl group , 2- (Perfluorodecyl) ethyl group, 2- (Perfluoro-3-methylbutyl) ethyl group, 3- (Perfluoro-3-methylbutyl) -2-hydroxypropyl group, 2- (Perfluoro-5-methyl) Hexyl) Ethyl group, 2- (perfluoro-5-methylhexyl) -2-hydroxypropyl group, 2- (perfluoro-7-methyloctyl) ethyl group, and 2- (perfluoro-7-methyloctyl)- 2-Hydroxypropyl group, etc. may be mentioned.

If R ¹² in formula (1) is a fluorine-substituted hydrocarbon group and the hydrocarbon group may be interrupted by —O—, one of the representative R ^12s is a fluoroalkyl ether group. Is.
For example, an Rf group (a) having a polyfluoroether structure represented by the following formula 1 can be mentioned.
-(X-O) _n -Y ... Equation 1
In formula 1, X is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorolated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and is in units of n. Representing the same group or different groups, Y is a hydrogen atom (only when a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Y) and a monovalent saturated carbon dioxide having 1 to 20 carbon atoms. It represents a hydrogen group or a fluorolated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 to 50. However, the total number of fluorine atoms in Equation 1 is 2 or more.

As an embodiment of X and Y in the formula 1, preferably X is a fluorolated alkylene group except for one hydrogen atom having 1 to 10 carbon atoms or a perfluorolated alkylene having 1 to 10 carbon atoms. It is a group and indicates the same group or a different group for each unit enclosed by n, and Y is an alkyl group or a fluorocarbonized group having 1 to 20 carbon atoms except for one hydrogen atom having 1 to 20 carbon atoms. Examples thereof include those showing up to 20 perfluorolated alkyl groups.

More preferably, X is a perfluorolated alkylene group having 1 to 10 carbon atoms, and the same group or a different group is used for each unit enclosed in n. Indicated by Y, those indicating a perfluorolated alkyl group having 1 to 20 carbon atoms can be mentioned.

In Equation 1, n represents an integer of 2 to 50. n is preferably 2 to 30, more preferably 2 to 15. When n is 2 or more, the liquid repellency is good. When n is 50 or less, the liquid-repellent group is likely to be detached in the exposed portion, and the liquid-friendly property becomes good.

Further, the total number of carbon atoms in the Rf group (a) having a polyfluoroether structure represented by the formula 1 is 2 or more, 2 to 50, 2 to 30, 2 to 18, 2 to 10, 4 to 10, 4 to. The order of 8 is preferable. In this range, the polymer which is the component (A) exhibits good liquid repellency.

Specific examples of X include -CF _2- , -CF ₂ CF _2- , -CF _{2 CF 2 CF 2-, -CF 2 CF (CF 3)-, -CF 2 CF 2 CF 2 CF 2 - , - .} CF ₂ CF ₂ CF (CF ₃ )-and CF ₂ CF (CF ₃ ) CF _2- .

Specific examples of Y include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ ,-(CF ₂ ) ₂ CF ₃ ,-(CF ₂ ) ₃ CF ₃ ,-(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₅ CF ₃ ,-(CF ₂ ) ₆ CF ₃ ,-(CF ₂ ) ₇ CF ₃ ,-(CF ₂ ) ₈ CF ₃ ,-(CF ₂ ) ₉ CF ₃ , and (CF ₂ ) ₁₁ CF ₃ ,-(CF ₂ ) ₁₅ CF ₃ can be mentioned.

A preferred embodiment of the Rf group (a) having a polyfluoroether structure represented by the formula 1 is the Rf group (a) represented by the formula 2.

-C _p-1 F _{2 (p-1)} -O- (C _p F _2p -O) _n-1 -C _q F _{2q + 1} ... Equation 2
In Equation 2, p indicates an integer of 2 or 3, and each unit enclosed by n is the same group, q indicates an integer of 1 to 20, and n indicates an integer of 2 to 50.

Specifically, as the Rf group (a) represented by the formula 2,
-CF ₂ O (CF ₂ CF ₂ O) _n-1 CF ₃ (n is 2-9),
-CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₆ F ₁₃ (n is 2 to 6),
-CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₃ F ₇ (n is 2 to 6)
Is preferably mentioned from the viewpoint of ease of synthesis.

The Rf groups (a) in the polymer which is the component (A) may be the same or different.

As described above, the portion of the polymer as the component (A) exposed to ultraviolet rays due to the acid generated from the photoacid generator (details will be described later) contained in the photoparent liquid repellent portion forming composition according to the present invention. An organic group is released from the structure of formula (1) (for example, as an alcohol molecule) to cause cross-linking.
In addition to the structure of the formula (1), the polymer of the component (A) can be heated between the polymers of the component (A) or between the polymer of the component (A) and the other polymer of the component (D). Can further contain a structural unit derived from the second monomer having a group (group (x)) capable of forming a covalent bond between the two (note that the cross-linking agent which may be added separately is the component (E). Explained in section).

（式中、Ｒ^１３はアルキル基、アルコキシ基、またはフェニル基を表す。）
これらのうち、基（ｘ）としては、ヒドロキシ基、カルボキシル基またはアミド基が好ましい。Preferably, the group (x) is at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the following formula (2). Is.

(In the formula, R ¹³ represents an alkyl group, an alkoxy group, or a phenyl group.)
Of these, the group (x) is preferably a hydroxy group, a carboxyl group or an amide group.

These thermally reactive sites can form a covalent bond with another polymer of component (A) or a polymer of component (B) via a direct bond or a linking group, and as such a linking group, Is it a divalent group selected from a linear alkylene group having 1 to 15 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, a cyclic alkylene group having 3 to 20 carbon atoms and a phenylene group? Alternatively, it is a group in which a plurality of the divalent groups are bonded. In this case, the bond between the divalent groups constituting the linking group and the bond between the linking group and the thermoreactive site include a single bond, an ester bond, an amide bond, a urea bond or an ether bond. When there are a plurality of divalent groups, the divalent groups may be the same or different, and when there are a plurality of bonds, the bonds may be the same or different.

Examples of the linear alkylene group having 1 to 15 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group and an n-octylene. Examples thereof include a group, an n-nonylene group, an n-decylene group, an n-undecylene group, an n-dodecylene group, an n-tridecylene group, an n-tetradecylene group and an n-pentadecylene group.

Examples of the branched alkylene group having 3 to 20 carbon atoms include an i-propylene group, an i-butylene group, an s-butylene group, a t-butylene group, a 1-methyl-n-butylene group and a 2-methyl-. n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, 1-ethyl -N-propylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n- Butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3 -Dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene In addition to a group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, etc., an alkylene having a number of carbon atoms up to 20 and branched at any position. The group etc. can be mentioned.

Examples of the cyclic alkylene group having 3 to 20 carbon atoms include a monocyclic alkylene group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group and a cyclooctylene group, and a norbornylene. Examples thereof include a polycyclic alkylene group such as a group, a tricyclodecylene group, a tetracyclododecylene group and an adamantylene group.

In the above formula (2), examples of the alkyl group represented by R ¹³ include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable.
Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group and an n-pentyl group. , 1-Methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-Dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group Group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl- n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2 -Trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl Group, n-octyl group, n-nonyl group, n-decanyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl Examples thereof include a group, an n-octadecyl group, an n-nonadecil group, an n-eicosyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.
Among them, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group and the like are preferable.

In the above formula (2), examples of the alkoxy group represented by R ¹³ include an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
Examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group and an n-pentoxy group. , 1-Methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-Dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl- n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2 , 2-Dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2, -trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n- Propoxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy Group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosadecyloxy group, cyclopropoxy group, cyclobutoxy group, Cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group and the like can be mentioned.
Among them, a methoxy group, an ethoxy group, an n-propoxy group and the like are preferable.

In addition to the structural unit derived from the first monomer represented by the formula (1), between the polymers of the component (A) or between the polymers of the component (A) and the polymer of the component (D) by heat. A group (group (x)) capable of forming a covalent bond between the groups, preferably a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and the above formula (2). As a method for synthesizing a copolymer containing a structural unit derived from a second monomer having at least one group (x) selected from the group consisting of the groups to be formed, the first monomer having the structure of the formula (1) and heat are used. A group (group (x)) capable of forming a covalent bond between the polymers of the component (A) or between the polymer of the component (A) and the polymer of the component (B). Has at least one group (x) selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the above formula (2). The method of polymerizing with a monomer is convenient.

As a monomer having at least one group (x) selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the above formula (2). , For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3 -Dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) acrylate, poly (propylene glycol) acrylate, poly (ethylene) Glycol) methacrylate, poly (propylene glycol) methacrylate, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and 5 -Hydroxy group-containing monomers such as methacryloyloxy-6-hydroxynorbornen-2-carboxylic-6-lactone; acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono-( Monomers having carboxyl groups such as 2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylicamide, and N- (carboxyphenyl) acrylamide; hydroxystyrene, N-( Monotyls having a phenolic hydroxy group such as hydroxyphenyl) methacrylicamide, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) maleimide, and N- (hydroxyphenyl) maleimide; acrylamide, methacrylicamide, N-methylacrylamide, Monomers having an amide group such as N, N-dimethylacrylamide, N, N-diethylacrylamide; 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxy Monomer having an alkoxysilyl group such as trimethoxysilane and 3-methacryloyloxytriethoxysilane; according to the above formula (2) such as 2-acetoacetoxyethyl acrylate and 2-acetoacetoxyethyl methacrylate (ethylene glycol monoacetate acetate monomethacrylate). Monomer having a group represented; Monomer having an isocyanate group such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate; 2-(0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate , 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, diethyl 2-((2- (methacryloyloxy) ethyl) carbamoyl) malonate and the like, examples thereof include monomers having a blocked isocyanate group.

The component (A) is a structural unit derived from the monomer represented by the formula (1), a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and the above formula (2). It can also be a polymer having a structural unit derived from a monomer having at least one group (x) selected from the group consisting of the represented groups, and a structural unit derived from a monomer other than the above.

Examples of the method for synthesizing such a copolymer include a monomer represented by the formula (1), a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and the above formula (2). A monomer having at least one group (x) selected from the group consisting of the groups represented by (hereinafter, hydroxy group, carboxyl group, amide group, alkoxysilyl group, isocyanate group, blocked isocyanate group, and the above formula (2). ) Is also referred to as a specific functional group 1), and a method of polymerizing a monomer other than the above (hereinafter, also referred to as a third monomer) is convenient.

The monomer represented by the formula (1) and the monomer having at least one group (x) are as described above. The above-mentioned third monomer means a monomer other than the first and second monomers.
Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
Hereinafter, specific examples of the third monomer will be given, but the present invention is not limited thereto.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-. Butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2 Examples thereof include -propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate and tert-. Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ Examples thereof include butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate and the like.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinylnaphthalene, vinylcarbazole, allylglycidyl ether, and 3-ethenyl-7-oxabicyclo [4.1.0] heptane.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

The amount of each monomer used to obtain the specific copolymer is 10 to 90 mol% of the monomer represented by the formula (1), a hydroxy group, a carboxyl group, an amide group, based on the total amount of all the monomers. It is preferable that the amount of the monomer having at least one group (x) selected from the group consisting of an alkoxysilyl group, an isocyanate group, a blocked isocyanate group and a group represented by the above formula (2) is 10 to 90 mol%. .. If the content of the monomer having the specific functional group 1 is less than 10 mol%, it may be difficult to impart sufficient thermosetting property, and it may be difficult to maintain the solvent resistance of the obtained cured film.
When the third monomer is used in combination to obtain the specific copolymer, the amount used is preferably 90 mol% or less based on the total amount of all the monomers.

The method for obtaining the specific copolymer used in the present invention is not particularly limited, and is, for example, in a solvent in which the first and second monomers, optionally the third monomer, the polymerization initiator and the like coexist, at 50 to 110 ° C. Obtained by polymerization reaction under temperature. At that time, the solvent used is not particularly limited as long as it dissolves the first and second monomers, the third monomer used if desired, the polymerization initiator and the like. Specific examples will be described in <Solvent> described later.
The specific copolymer obtained by the above method is usually in the state of a solution dissolved in a solvent.

Further, the solution of the specific copolymer obtained by the above method is put into diethyl ether or water under stirring to reprecipitate, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. It can be dried at room temperature or dried by heating to obtain a powder of a specific copolymer. By the above operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

In the present invention, the specific copolymer may be used in the form of a powder or in the form of a solution in which the purified powder is redissolved in a solvent described later.

Further, in the present invention, the specific copolymer of the component (A) may be a mixture of a plurality of types of specific copolymers.

<Ingredient (B)>
The photoparent liquid-repellent portion forming composition used in the present invention further contains a photoacid generator as a component (B) in addition to the component (A) and the solvent.

The photoacid generator of the component (B) is not particularly limited as long as it is a compound that photodecomposes to generate an acid when irradiated with ultraviolet rays.

Examples of the acid generated when the photoacid generator is photodecomposed include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentansulfonic acid, octanesulfonic acid, benzenesulfonic acid, and p-. Toluene sulfonic acid, campha sulfonic acid, trifluoromethane sulfonic acid, p-phenol sulfonic acid, 2-naphthalene sulfonic acid, mesitylene sulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene Sulfonic acid, 1H, 1H, 2H, 2H-perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzene sulfonic acid and other sulfonic acids. Examples thereof include acid or its hydrate and salt.

Examples of compounds that generate acid by light include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-. P-toluenetris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p- Toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate , N-ethyl-p-toluenesulfonicamide, compounds represented by the following formulas [PAG-1] to [PAG-41], and the like.

The content of the component (B) in the photofriendly liquid-repellent portion forming composition is preferably 100 parts by mass when the total mass of the polymer of the component (A) and the other polymer of the component (D) described later is 100 parts by mass. It is 0.1 part by mass to 20 parts by mass, more preferably 0.5 part by mass to 20 parts by mass, further preferably 1 part by mass to 15 parts by mass, and most preferably 5 parts by mass to 15 parts by mass. If the content of the component (B) is more than 20 parts by mass, the storage stability of the composition may decrease.

<Ingredient (C)>
The photophilic liquid-repellent portion-forming composition used in the present invention does not dissolve in the composition and in the film after film formation as the component (C) in addition to the component (A), the component (B) and the solvent. Further stable fine particles may be contained. The fine particles of the component (C) have a role of forming a fine uneven shape on the surface of the cured film of the present embodiment to amplify the lipophilicity of the parent liquid portion and the liquid repellent property of the liquid repellent portion. Further, depending on the structure of the fine particles, the cured film may be provided with stability such as solvent resistance and heat resistance, and optical characteristics such as transparency, light diffusivity, and refractive index control.

The fine particles of the component (C) are not particularly limited as long as they play the above-mentioned roles, and examples thereof include organic fine particles and inorganic fine particles.

The shape of the organic / inorganic fine particles is not particularly limited, but may be, for example, a bead-shaped substantially spherical shape, a chain shape in which beads are connected, or an amorphous shape such as powder. The average particle size of the organic fine particles used in the present invention is preferably 5 nm to 10 μm. Here, the average particle size (μm) is a 50% volume diameter (median diameter) obtained by measuring by a laser diffraction / scattering method based on the Mie theory.

Examples of the organic fine particles include polymethylmethacrylate particles (PMMA particles), silicone particles, polystyrene particles, polycarbonate particles, acrylic styrene particles, benzoguanamine particles, melamine particles, polyolefin particles, polyester particles, polyamide particles, polyimide particles, and polyfluors. Examples thereof include ethylene chemicalized particles.

Commercially available products can be preferably used as the organic fine particles. For example, Techpolymer (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, etc. ARX series, AFX series, MB series, MBP series, MB-C series, ACX series, ACP series [above, manufactured by Sekisui Kasei Kogyo Co., Ltd.]; Tospearl (registered trademark) series [momentive] -Performance Materials Japan (same)]; Epostal (registered trademark) series, MA series, ST series, MX series [above, Nippon Catalyst Co., Ltd.]; Optobeads (registered trademark) series [ Nissan Chemical Industry Co., Ltd.]; Flow beads series [Sumitomo Seika Co., Ltd.]; Trepearl (registered trademark) PPS, PAI, PES, EP [above, Toray Co., Ltd.]; 3M (registered) Trademark) Dynion TF Micro Powder Series [manufactured by 3M]; Chemisnow (registered trademark) MX series, MZ series, MR series, KMR series, KSR series, MP series, SX series, SGP series [above , Soken Kagaku Co., Ltd.]; Tuftic (registered trademark) AR650 series, AR-750 series, FH-S series, A-20, YK series, ASF series, HU series, F series, Same C series, same WS series [above, manufactured by Toyo Spinning Co., Ltd.]; Art Pearl (registered trademark) GR series, same SE series, same G series, same GS series, same J series, same MF series, same BE series [ As described above, [manufactured by Negami Kogyo Co., Ltd.]; Shinetsu Silicone (registered trademark) KMP series [manufactured by Shinetsu Kagaku Kogyo Co., Ltd.] and the like can be used.

Examples of the inorganic fine particles include silica, aluminum oxide, aluminum hydroxide, talc, calcium carbonate, mica, magnesium hydroxide, tin oxide, zirconium oxide, titanium oxide and the like.

Among these inorganic fine particles, silica is preferable, and colloidal silica particles having an average primary particle diameter of 5 nm to 100 nm are particularly preferable. Here, the average primary particle size is an average value of the primary particle size measured by observation with a transmission electron microscope.

Silica sol can be used as the colloidal silica particles described above. As the silica sol, an aqueous silica sol produced by a known method using an aqueous sodium silicate solution as a raw material or an organic solvent-dispersed silica sol obtained by substituting water as a dispersion medium of the aqueous silica sol with an organic solvent can be used.

Further, it is obtained by hydrolyzing and condensing an alkoxysilane such as methyl silicate or ethyl silicate in an organic solvent such as alcohol in the presence of a catalyst (for example, an alkaline catalyst such as ammonia, an organic amine compound or sodium hydroxide). It is also possible to use an organosilica sol in which the silica sol or the dispersion medium of the silica sol is replaced with another organic solvent.

Examples of commercial products of the above organosilica sol include, for example, trade name MA-ST-S (methanol-dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.) and trade name MT-ST (methanol-dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.). ), Product name MA-ST-UP (methanol-dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), Product name MA-ST-M (methanol-dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), Product name MA-ST- L (methanol-dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name IPA-ST-S (isopropanol dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name IPA-ST (isopropanol dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.) (Co., Ltd.), trade name IPA-ST-UP (isopropanol dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name IPA-ST-L (isopropanol dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name IPA -ST-ZL (isopropanol dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name NPC-ST-30 (n-propyl cellosolve dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name PGM-ST (1- Methoxy-2-propanol dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd., trade name DMAC-ST (dimethylacetamide dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name XBA-ST (xylene / n-butanol mixed solvent) Dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd., trade name EAC-ST (ethyl acetate dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name PMA-ST (propylene glycol monomethyl ether acetate dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.) (Made by Co., Ltd.), trade name MEK-ST (Methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name MEK-ST-UP (Methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name MEK-ST -L (Methyl Ethyl Ketone Dispersed Silica Sol, manufactured by Nissan Chemical Industry Co., Ltd.) and trade name MIBK-ST (Methyl Isobutyl Ketone Dispersed Silica Sol, manufactured by Nissan Chemical Industry Co., Ltd.) and the like can be mentioned, but are not limited thereto.
One type of these organic and inorganic fine particles may be used alone, or two or more types may be used in combination.

When the component (C) is contained in the photofriendly liquid-repellent portion forming composition, the content is 100 parts by mass of the total mass of the component (A), the component (B), the component (D) and the component (E) described later. , It is preferably 20 parts by mass to 900 parts by mass, more preferably 60 parts by mass to 700 parts by mass, and further preferably 150 parts by mass to 400 parts by mass. When the content of the component (C) is less than 20 parts by mass, sufficient unevenness may not be formed on the surface of the cured film. Further, when the content of the component (C) is more than 900 parts by mass, the film-forming property of the cured film may be deteriorated.

<(D) component>
The photoparent liquid-repellent portion forming composition used in the present invention can take the form of a so-called polymer blend by mixing other polymers as the component (D) in addition to the component (A) and the component (B). ..
By appropriately adjusting the structure and the like of the polymer (component (A), component (D), and other polymers) contained in this polymer blend, the cured film is formed in the thickness direction in the film. Since it is possible to generate a concentration gradient of each polymer, it can be used as a useful means.

For example, the change in liquid repellency is a problem only on the film surface. Therefore, from this viewpoint, the polymer having an alkyl group desorbed by the effect of the acid generator used in the present invention is the upper layer of the cured film. It only needs to be present in the (surface layer).
The blending ratio of each component will be described in the section "Preparation of Photo-Repellent Liquid Repellent Part Forming Composition".

By selecting the component (D) having an appropriate structure and performing the above polymer blending, effects such as improvement of film forming property and improvement of adhesion to a substrate can be imparted.

As described above, in order to form the lower layer of the cured film as a low liquid repellent layer and the upper layer as a pro-liquid repellent conversion layer, it is possible to sequentially stack these layers, but the operation is complicated. ..
At this time, the low liquid-repellent material and the material of the pro-liquid-repellent conversion layer (that is, the polymer of the component (A)) are mixed, and at that time, the polarity or molecular weight of the upper layer material is compared with that of the lower layer. If the size is small, the above-mentioned concentration gradient (the layer referred to here) is exhibited because the upper layer material moves to the surface and forms a layer while the mixed solution is applied to the substrate and dried to evaporate the solvent. Separation) can be easily controlled.

The most preferable material for forming the film capable of forming the lower layer is an acrylic polymer.
Other materials that can be used as the underlayer material include common organic polymers such as epoxy resin, acrylic resin, polypropylene, polyvinyl alcohol, polyvinylphenol, polyisobutylene, polyester and polyimide.

Further, when the polymer blend is used, for example, in an application requiring a film thickness of about 400 nm, in order to prevent large in-plane variation in the surface physical properties of the cured film, the polymer of the component (A) is used. It is preferably contained at least 5% by weight or more.

In the photoparent liquid-repellent portion forming composition used in the present invention, when ^R12 in the formula (1) of the component (A) is a hydrocarbon group substituted with fluorine, that is, the component (A) contains a fluorine-containing weight. In the case of a coalescence, it is preferable that the composition contains another polymer as the component (D) from the viewpoint of film forming property. At that time, the fluorine content of the other polymer as the component (D) is preferably such that the fluorine content based on the total weight of the polymer is not less than the component (A). That is, the polymer (D) component is a poor fluorine polymer that does not contain or has a trace amount of fluorine atoms, and when the composition is applied onto the substrate, it is relative to the substrate side of the coating layer. It is preferable that it is present in a high concentration. Preferably, the fluorine content of the component (D) in the polymer is less than 5% by weight based on the total weight of the polymer.

When R ¹² in the formula (1) of the component (A) is a hydrocarbon group substituted with fluorine, that is, when the component (A) is a fluorine-containing polymer, the unit structure of the component (D) is As such, a polymer having an N-alkoxymethyl group is preferable.

The N of the N-alkoxymethyl group, that is, the nitrogen atom, is the position adjacent to the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, and the nitrogen atom of the nitrogen-containing heterocycle. Examples thereof include nitrogen atoms bonded to. Therefore, the N-alkoxymethyl group includes nitrogen bonded to the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, and the nitrogen atom of the nitrogen-containing heterocycle. Examples thereof include a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from an atom or the like.

The monomer giving the N-alkoxymethyl group may be any one having the above group, but a compound in which ^R12 is an alkyl group in the above formula (1) is preferable.

The polymer of the component (D) has a structure derived from a monomer having a group (group (x)) capable of forming a covalent bond with another polymer of the component (D) or a polymer of the component (A) by heat. Can contain units.
For example, the component (D) is a group (x) selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the above formula (2). ) (Hereinafter, also referred to as a specific functional group 2) can be contained.

Examples of the polymer compound as the component (D) include acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, and polyalkylene imines. , Polyallylamine, celluloses (cellulose or a derivative thereof), polymers having a linear structure or a branched structure such as phenol novolac resin, cyclic polymers such as cyclodextrins and the like.

Preferred examples of the polymer compound as the component (D) include acrylic polymers, cyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, and phenol novolac resins.

The acrylic polymer which is a preferable example of the polymer compound of the component (D) is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, and a vinyl compound. , A polymer obtained by polymerizing a monomer containing the group (x) or a mixture thereof, and the type of the main chain skeleton and side chains of the polymer constituting the acrylic polymer is not particularly limited.

As a monomer having at least one group (x) selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the above formula (2). Including preferable examples, the "second monomer" mentioned in the section of the component (A) above can be mentioned.

Further, in the present invention, when synthesizing an acrylic polymer which is an example of the component (D), a monomer having no specific functional group 2 can be used in combination as long as the effect of the present invention is not impaired.

Specific examples of such a monomer include the "third monomer" mentioned in the section of the component (A) above, including a preferable example.

The amount of the second monomer used to obtain the acrylic polymer which is an example of the component (D) is 2% by weight based on the total amount of all the monomers used to obtain the acrylic polymer which is the component (D). It is preferably 100% by weight. If the second monomer is too small, the coatability of the obtained cured film may be insufficient.
When the third monomer is used in combination to obtain the acrylic polymer, the amount used is preferably 98% by weight or less based on the total amount of all the monomers.

The method for obtaining the acrylic polymer as an example of the component (D) is not particularly limited, but for example, in a solvent in which a second monomer, a third monomer if desired, a polymerization initiator and the like coexist, the temperature is 50 ° C. or higher. It is obtained by a polymerization reaction at a temperature of 110 ° C. At that time, the solvent used is not particularly limited as long as it dissolves the second monomer, the third monomer, the polymerization initiator and the like, if desired. Specific examples will be described in the section <Solvent> described later.

The acrylic polymer, which is an example of the component (D) obtained by the above method, is usually in the state of a solution dissolved in a solvent.

Further, the solution of the acrylic polymer, which is an example of the component (D) obtained by the above method, is put into diethyl ether or water under stirring to reprecipitate, and the generated precipitate is filtered and washed. It can be dried at room temperature or heat-dried under normal pressure or reduced pressure to obtain a powder of an acrylic polymer as an example of the component (D). By the above operation, the polymerization initiator and the unreacted monomer coexisting with the acrylic polymer which is an example of the component (D) can be removed, and as a result, the acrylic polymer which is an example of the purified component (D) can be removed. Powder is obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

The acrylic polymer, which is a preferable example of the component (D), preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and 5,000 to 100. It is more preferably 000. If the weight average molecular weight is more than 200,000 and is excessive, the solubility in a solvent may be lowered and the handleability may be lowered, and if the weight average molecular weight is less than 3,000 and too small, heat may be deteriorated. At the time of curing, the curing may be insufficient and the solvent resistance and heat resistance may decrease.

Cyclodextrins which are preferable examples of the polymer compound of the component (D) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin; methyl-α-cyclodextrin and methyl-β-cyclo. Dextrin, and methylated cyclodextrins such as methyl-γ-cyclodextrin; hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-Hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-Hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β -Cyclodextrin, hydroxyalkylcyclodextrin such as 2,3-dihydroxypropyl-γ-cyclodextrin and the like can be mentioned, and for example, hydroxyalkylcyclodextrin is preferable.

Preferred examples of the celluloses as the polymer compound of the component (D) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose. Examples thereof include cellulose, and hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

Next, as the polyether polyol which is a preferable example of the polymer compound of the component (D), propylene oxide or polyethylene glycol is added to polyhydric alcohols such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol and sorbitol. , Polypropylene glycol and the like are added. Specific examples of the polyether polyol include ADEKA's ADEKA polyether P series, G series, EDP series, BPX series, FC series, CM series, and Nichiyu Uniox (registered trademark) HC-40, HC-60, ST. -30E, ST-40E, G-450, G-750, Uniol® TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB- 400, Nonion (registered trademark) LT-221, ST-221, OT-221 and the like can be mentioned.

As a polyester polyol which is a preferable example of the polymer compound of the component (D), polyvalent carboxylic acids such as adipic acid, sebacic acid and isophthalic acid and diols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol and polypropylene glycol are used. Can be mentioned. Specific examples of the polyester polyol include Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668 manufactured by DIC. , OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD -X-2555, OD-X-2560, Clare polyols P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, Examples thereof include F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like.

Examples of the polycarbonate polyol which is a preferable example of the polymer compound of the component (D) include those obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like. Specific examples of the polycarbonate polyol include Daicel Chemical's Praxel (registered trademark) CD205, CD205PL, CD210, CD220, Kuraray's polycarbonate diols C-590, C-1050, C-2050, C-2090, C-3090 and the like. ..

Examples of the polycaprolactone polyol which is a preferable example of the polymer compound of the component (D) include those obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of the polycaprolactone polyol include Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568 manufactured by DIC, and Praxel® 205, L205AL, 205U, 208, 210 manufactured by Daicel Chemical Co., Ltd. , 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320 and the like.

Examples of the phenol novolak resin, which is a preferable example of the polymer compound of the component (D), include a phenol-formaldehyde polycondensate.

In the photophilic liquid-repellent portion-forming composition used in the present invention, the compound of the component (D) may be used in the form of a powder or in the form of a solution obtained by redissolving the purified powder in a solvent described later.

Further, in the photoparent liquid-repellent portion forming composition used in the present invention, the component (D) may be a single component or a mixture of a plurality of species of the compounds exemplified as the component (D). good.

The content of the component (D) in the photoparent liquid-repellent portion forming composition used in the present invention is based on 10 parts by mass of the component (A) when the component (A) is a polymer containing fluorine. 5, 95 parts by mass, 30 to 95 parts by mass, 50 to 95 parts by mass, 60 to 95 parts by mass, and 80 to 95 parts by mass are preferable in this order. (D) There is a problem that the image forming ability is lowered when the content of the component is excessive. If it is too small, there is a problem that the film-forming property is deteriorated.

<(E) component>
The photoparent liquid-repellent portion-forming composition used in the present invention can further contain a compound having two or more groups capable of thermally reacting with the group (x) as the component (E). The component (E) is a cross-linking agent, which is optionally introduced into the composition. For example, it is a compound having a structure capable of forming a bridging structure by a thermal reaction with a hydroxy group or the like contained in the components (A) and (D).

Specific examples are given below, but the present invention is not limited to these. The heat cross-linking agent is, for example, a (E-1) phenoplast-based compound, (E-2) epoxy-based compound, (E-3) a cross-linking compound having two or more isocyanate groups or blocked isocyanate groups per molecule. (E-4) A crosslinkable compound having two or more merdrumic acid structures per molecule is preferable. When the group (x) is an isocyanate group, a blocked isocyanate group, or an alkoxysilyl group, a compound having two or more groups (x) per molecule can be used as the cross-linking agent. These cross-linking agents can be used alone or in combination of two or more.

Specific examples of the (E-1) phenoplast-based compound include 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) cresol, and 2,6-bis (hydroxymethyl) -4. -Methoxyphenol, 3,3', 5,5'-tetrakis (hydroxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4' -(1-Methylethylidene) bis [2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis [2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene) bis [2,6-bis (hydroxymethyl) phenol], 4,4'-methylenebis [2,6-bis (hydroxymethyl) phenol], 2,6-bis (methoxymethyl) phenol, 2,6-bis (methoxy) Methyl) cresol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 3,3', 5,5'-tetrakis (methoxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis ( 2-methoxy-5-methylbenzenemethanol), 4,4'-(1-methylethylidene) bis [2-methyl-6-methoxymethylphenol], 4,4'-methylenebis [2-methyl-6-methoxymethyl] Phenol], 4,4'-(1-methylethylidene) bis [2,6-bis (methoxymethyl) phenol], 4,4'-methylenebis [2,6-bis (methoxymethyl) phenol], etc. Is done. It can also be obtained as a commercially available product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA ( As mentioned above, Asahi Organic Materials Industry Co., Ltd.) and the like can be mentioned.

These crosslinkable compounds can be used alone or in combination of two or more.

（式中、ｋは２～１０の整数、ｍは０～４の整数を示し、Ｒ^２１はｋ価の有機基を表す）Further, the photoparent liquid-repellent portion forming composition used in the present invention can contain an epoxy-based compound as the component (E-2).
As the epoxy compound, for example, a crosslinkable compound represented by the formula (e2) can be contained.

(In the formula, k is an integer of 2 to 10, m is an integer of 0 to 4, and R ²¹ is an organic group having a k valence).

Such a component is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by the formula (e2). Specific examples thereof include the following formulas E-2-1 and E-2-2, commercial products shown below, and the like.

Commercially available products include Eporide GT-401, GT-403, GT-301, GT-302, Selokiside 2021, Selokiside 3000 (trade name manufactured by Daicel Chemical Industry Co., Ltd.), and Denacol, which is an alicyclic epoxy resin. EX-252 (trade name made by Nagase ChemteX Corporation), CY175, CY177, CY179 (above, product name made by CIBA-GEIGY AG), Araldite CY-182, CY-192, CY-184 (above). , CIBA-GEIGY AG product name), Epicron 200, 400 (product name of DIC Co., Ltd.), Epicoat 871, 872 (product name of Yuka Shell Epoxy Co., Ltd.), ED -5661, ED-5662 (hereinafter, product name manufactured by Ceranies Coating Co., Ltd.), and the like can be mentioned. Further, a polymer obtained by using Cyclomer M-100 (trade name manufactured by Daicel Corporation) or the like as a raw material can be used.

（式中、ｐは２～１０の整数を示し、Ｒ^３１はｐ価の有機基を表す。）Further, as the epoxy compound, for example, a compound having a partial structure of the following formula (E-2-3) can be used.

(In the formula, p represents an integer of 2 to 10, and R ³¹ represents a p-valent organic group.)

The compound is not particularly limited as long as it has an oxylan structure represented by the formula (E-2-3). Specific examples thereof include the following formula (E-2-4) and commercially available products shown below.

As commercially available products, as bisphenol A type epoxy resin, for example, "Epicoat 828", "Epicoat 834", "Epicoat 1001", "Epicoat 1004" (trade name, all manufactured by Japan Epoxy Resin), "Epiclon 850" , "Epoxylon 860", "Epoxylon 4055" (trade name, all manufactured by Dainippon Ink and Chemicals Co., Ltd.) and the like. Examples of the bisphenol F type epoxy resin include "Epicoat 807" (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) and "Epiclon 830" (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.). Examples of the phenol novolac type epoxy resin include "Epiclon N-740", "Epiclon N-770", "Epiclon N-775" (trade name, all manufactured by Dainippon Ink and Chemicals Co., Ltd.), "Epicoat 152". , "Epicoat 154" (trade name, both manufactured by Japan Epoxy Resin Co., Ltd.) and the like. Examples of the cresol novolac type epoxy resin include "Epiclon N-660", "Epiclon N-665", "Epiclon N-670", "Epiclon N-673", "Epiclon N-680", and "Epiclon N-695". , "Epoxy N-665-EXP", "Epoxy N-672-EXP" (trade name, all manufactured by Dainippon Ink and Chemicals Co., Ltd.) and the like. Examples of the glycidylamine type epoxy resin include "Epiclon 430", "Epiclon 430-L" (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.), "TETRAD-C", and "TETRAD-X" (trade name). , All manufactured by Mitsubishi Gas Chemical Company, Inc., "Epicoat 604", "Epicoat 630" (trade name, all manufactured by Japan Epoxy Resin Co., Ltd.), "Sumiepoxy ELM120", "Sumiepoxy ELM100", "Sumiepoxy ELM434" , "Sumiepoxy ELM434HV" (trade name, all manufactured by Sumitomo Chemical Co., Ltd.), "Epototo YH-434", "Epototo YH-434L" (trade name, all manufactured by Toto Kasei Co., Ltd.), "Araldite MY" -720 "(trade name, manufactured by Asahi Ciba Co., Ltd.) and the like can be mentioned. Further, a polymer obtained by using glycidyl methacrylate or the like as a raw material can be used.

These crosslinkable compounds can be used alone or in combination of two or more.

The component (E-3) is not particularly limited as long as it is a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule. Specific examples thereof include commercially available products shown below.
Commercially available products include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, B-5010 (above, Mitsui Chemicals). (Manufactured by Asahi Kasei Chemicals Co., Ltd.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (all manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like.
Further, obtained from a monomer having a blocked isocyanate group such as Calends (registered trademark) AOI, Calends MOI, Calends MOI-BM, Calends MOI-BP, Calends MOI-DEM (all manufactured by Showa Denko KK) as a raw material. The polymer to be used can be used.

（式中、Ｗ_１はｋ_１価の有機基を表す。Ｖ_１は、－Ｈ、－ＯＨ、－ＳＲ、－ＯＲまたは－ＮＨＲを表し、Ｒは、ベンゼン環、シクロヘキサン環、ヘテロ環、フッ素、エーテル結合、エステル結合、アミド結合を任意の場所に含んでいてもよい炭素原子数が１～３５の一価の有機基を表す。ｋ_１は、１～８の整数を表す。）The component (E-4) is a crosslinkable compound having two or more Meldrum's acid structures per molecule. Among these, the compound represented by the following formula [A] is preferable.

(In the formula, W ₁ represents a k _- valent organic group. V ₁ represents -H, -OH, -SR, -OR or -NHR, and R is a benzene ring, a cyclohexane ring, a hetero ring, or fluorine. , An ether bond, an ester bond, or an amide bond may be contained at any place. A monovalent organic group having 1 to 35 carbon atoms is represented. K ₁ represents an integer of 1 to 8).

When k ₁ is 2, W ₁ is preferably a linear, branched or cyclic alkylene of C ₂ to C ₁₀ . Such compounds are described in International Patent Application Publication No. WO2012 / 091089, including the production method.
As such a compound, a compound represented by the following formula E4 is particularly preferable.

The cross-linking agent represented by the above formula [A] may be used alone or in combination of two or more.

When the group (x) is an isocyanate group, a blocked isocyanate group, or an alkoxysilyl group, a compound having two or more groups (x) per molecule can be used as the cross-linking agent.
Specific examples thereof include pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, dipropylene glycol, adipic acid, adipamide, 1- (4- (2- (4- (3-oxo-butyl) -phenoxy)-. Ethoxy) -phenyl) -butane-1,3-dione, 1,4-butanediol diacetacetate and the like can be mentioned.
Further, among the polymers defined as the component (D) as the polymer compound having two or more groups (x) per molecular chain, the polymer having two or more groups (x) per molecular chain shall be used. You can also.

Among these, a blocked isocyanate obtained from a monomer of diethyl 2-((2- (methacryloyloxy) ethyl) carbamoyl) malonate, a crosslinkable compound having a Meldrum's acid structure from the viewpoint of reactivity and solvent resistance, as a raw material. Polymers with groups are preferred.

When the component (E) is added as the cross-linking agent, the content is 3 to 50 parts by mass, preferably 7 to 40 parts by mass, more preferably 7 to 40 parts by mass with respect to 100 parts by mass of the total of the components (A) and (D). Is 10 to 30 parts by mass. When the content of the crosslinkable compound is low, the density of the crosslinks formed by the crosslinkable compound is not sufficient, so that the effect of improving the solvent resistance after pattern formation may not be obtained. On the other hand, when it exceeds 50 parts by mass, an uncrosslinked crosslinkable compound is present, and the heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation are lowered, and the photoparent liquid repellent part is also present. The storage stability of the forming composition may deteriorate.

<Other additives>
The photoparent liquid-repellent portion-forming composition used in the present invention may contain other additives as long as the effects of the present invention are not impaired.
As other additives, for example, a sensitizer can be contained. The sensitizer is effective in promoting the photoreaction of the cured film forming composition of the present invention when forming the cured film of the present invention.

Examples of the sensitizer include derivatives such as benzophenone, anthracene, anthraquinone and thioxanthone, nitrophenyl compounds and the like. Of these, N, N-diethylaminobenzophenone, which is a derivative of benzophenone, and 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaften, 4-nitrobiphenyl, 4-nitrocarbic acid, 4-nitrophenyl compound, which are nitrophenyl compounds. Nitrostilbene, 4-nitrobenzophenone and 5-nitroindole are particularly preferred.
These sensitizers are not particularly limited to those described above. These can be used alone or in combination of two or more compounds.

In the embodiment of the present invention, the ratio of the sensitizer used is 100 parts by mass of the total amount of the component (A), the component (B) and, if necessary, the component (C), the component (D) and the component (E). It is preferably 0.1 part by mass to 20 parts by mass, and more preferably 0.2 part by mass to 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained, and if it is too large, the transmittance of the formed cured film may decrease or the coating film may become rough. I have something to do.

Further, the photophilic liquid-repellent portion-forming composition used in the present invention may contain, as other additives, a silane coupling agent, a surfactant, a rheology adjuster, a pigment, a dye, as long as the effect of the present invention is not impaired. It can contain a storage stabilizer, an antifoaming agent, an antioxidant and the like.

<Solvent>
The photoparent liquid-repellent portion-forming composition used in the present invention is often used in a dispersed liquid state dissolved and dispersed in a solvent. The solvent used at that time is one that disperses and dissolves the component (A) and the component (B), and if necessary, the component (C), the component (D), the component (E) and / or other additives. The type and structure of the solvent are not particularly limited as long as they have such a dissolving ability.

Specific examples of the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether. Acetate, propylene glycol propyl ether acetate, cyclopentyl methyl ether, isopropyl alcohol, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone , 2-Hydroxypropionate, 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , 3-ethoxypropionate ethyl, 3-ethoxypropionate methyl, pyruvate methyl, pyruvate ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and Examples thereof include N-methylpyrrolidone.

These solvents can be used alone or in combination of two or more. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, 3-methoxypropion. Ethyl acetate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate are more preferable because they have good film forming properties and high safety.

When the component obtained by removing the solvent from the photoparent liquid-repellent portion forming composition used in the present invention is regarded as a solid content, the ratio of the solid content to the composition is, for example, 1% by mass or more and 30% by mass or less.

<Preparation of photoparent liquid repellent part forming composition>
The photoparent liquid-repellent portion-forming composition used in the present invention comprises a polymer containing a structural unit derived from a first monomer having the structure of the above formula (1) as a component (A) and a photoacid as a component (B). Contains a generator and a solvent. Further, if necessary, the polymer has fine particles as the component (C) and a polymer other than the component (A) as the component (D), and the fluorine content based on the total weight standard of the polymer is less than or equal to the component (A). It is possible to contain the polymer which is the above and a cross-linking agent as the component (E). Then, other additives can be contained as long as the effects of the present invention are not impaired.

Preferred examples of the photoparent liquid-repellent portion forming composition used in the present invention are as follows.
[1]: As the component (A), a polymer containing a structural unit derived from the first monomer having the structure of the above formula (1), and 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (A). A photo-friendly liquid-repellent portion-forming composition containing a photoacid generator of the component (B) and a solvent.
[2]: As the component (A), a polymer containing a structural unit derived from the first monomer having the structure of the above formula (1), and 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (A). 20 to 900 parts by mass of fine particles and a solvent with respect to 100 parts by mass of the total amount of the photoacid generator of the component (B) and the component (C) of the component (A) and the component (B). A photo-friendly liquid-repellent portion-forming composition to be contained.
[3]: As the component (A), a polymer containing a structural unit derived from the first monomer having the structure of the above formula (1) and a polymer other than the component (A) as the component (D) are (A). ) Component: Containing in a mass ratio of component (D) 5-67: 95-33, 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (D). 20 to 900 parts by mass of fine particles with respect to 100 parts by mass of the total amount of the photoacid generator of the component (B) and the total amount of the component (A), the component (B) and the component (D) as the component (C). And a photoparent liquid-repellent portion forming composition containing a solvent.
[4]: As the component (A), a polymer containing a structural unit derived from the first monomer having the structure of the above formula (1), and 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (A). The photoacid generator of the component (B), the cross-linking agent of the component (E) in an amount of 3 to 50 parts by mass with respect to 100 parts by mass of the component (A), and the component (A) as the component (C). And a photoparent liquid repellent portion forming composition containing 20 to 900 parts by mass of fine particles and a solvent with respect to 100 parts by mass of the total amount of the component (B) and the component (E).
[5]: As the component (A), a polymer containing a structural unit derived from the first monomer having the structure of the above formula (1) and a polymer other than the component (A) as the component (D) are (A). ) Component: Containing in a mass ratio of component (D) 5-67: 95-33, 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (D). The photoacid generator of the component (B), the cross-linking agent of the component (E) in an amount of 3 to 50 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (D), and (C). ) Containing 20 to 900 parts by mass of fine particles and a solvent with respect to 100 parts by mass of the total amount of the component (A), the component (B), the component (D) and the component (E). Liquid part forming composition.

The blending ratio, preparation method, etc. when the photoparent liquid-repellent portion forming composition used in the present invention is used as a solution will be described in detail below.
The ratio of the solid content in the photoparent liquid-repellent portion forming composition used in the present invention is not particularly limited as long as each component is uniformly dissolved and dispersed in the solvent, but is 1% by mass to 80% by mass. %, Preferably 2% by mass to 60% by mass, and more preferably 3% by mass to 40% by mass. Here, the solid content refers to a composition obtained by removing the solvent from all the components of the photoparent liquid-repellent portion forming composition.

The method for preparing the photoparent liquid-repellent portion-forming composition used in the present invention is not particularly limited. As a preparation method, for example, the component (B), the component (C), the component (D), and the component (E) are mixed in a solution of the component (A) dissolved in a solvent at a predetermined ratio and uniformly dispersed. Examples thereof include a method of making a liquid, or a method of further adding and mixing other additives as necessary at an appropriate stage of this preparation method.

In the preparation of the photoparent liquid-repellent portion forming composition used in the present invention, the solution of the specific copolymer obtained by the polymerization reaction in the solvent can be used as it is. In this case, for example, the component (B), the component (C), the component (D), the component (E), and other optional components are added to the solution prepared by preparing the polymer of the component (A) for uniform dispersion. Make it a liquid. At this time, an additional solvent may be added for the purpose of adjusting the concentration. At this time, the solvent used in the process of preparing the component (A) and the solvent used for adjusting the concentration of the photoparent liquid-repellent portion forming composition may be the same or different.

Further, it is preferable that the prepared dispersion liquid of the photoparent liquid-repellent portion forming composition is used after being filtered using a filter having a pore size of about 0.2 to 20 μm or the like.

<Manufacturing method of coating film and cured film>
The photo-friendly liquid-repellent portion-forming composition used in the present invention is subjected to a dip method, spin, or the like on a general-purpose plastic substrate such as polypropylene, polyethylene, polycarbonate, polyethylene terephthalate, polyether sulfone, polyethylene naphthalate, or polyimide, or a glass substrate. By applying by a coating method, transfer printing method, roll coating method, inkjet method, spray method, brush coating, etc., and then drying and heat-treating this coating film with a hot plate or oven, the underlayer film for image formation can be obtained. A cured film for patterning that can be used as an insulating film is formed.

The method of the heat treatment is not particularly limited, and examples thereof include a method of performing the heat treatment in an appropriate atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or in a vacuum, using a hot plate or an oven.
The firing temperature is preferably 200 ° C. or lower in order to suppress the decomposition of the structure of the formula (1) of the component (A) and the photoacid generator of the component (B).
The firing may be carried out by subjecting the temperature to two or more steps. The uniformity of the film obtained by firing in stages can be further improved.

When the cured film produced as described above is used as an image forming underlayer film, if the film thickness is too thin, the patterning property after ultraviolet irradiation is deteriorated, and if the film thickness is too thick, the surface uniformity is impaired. Therefore, the film thickness is preferably 5 nm to 1,000 nm, more preferably 10 nm to 800 nm, and most preferably 20 nm to 500 nm.

Further, the cured film can also function as an insulating film if the insulating property is sufficiently high. In that case, the cured film is arranged directly on the gate electrode and used as a gate insulating film in, for example, an organic FET element. At that time, it is desirable that the film thickness of the cured film is thicker than that when it is used as the above-mentioned image forming underlayer film for the purpose of ensuring the insulating property. The film thickness is preferably 20 nm to 1,000 nm, more preferably 50 nm to 800 nm, and most preferably 100 nm to 500 nm.

<Use as an image forming underlayer film: Method for manufacturing an image forming electrode>
An image forming electrode can be manufactured by irradiating the image forming lower layer film used in the present invention with ultraviolet rays in a pattern and then applying an image forming solution described later.

In the present invention, the method of irradiating the above-mentioned underlayer film for image formation in a pattern is not particularly limited, but for example, a method of irradiating through a mask on which an electrode pattern is drawn, an electrode pattern using laser light, etc. The method of drawing is mentioned.
The material and shape of the mask are not particularly limited as long as the region requiring the electrode transmits ultraviolet rays and the other region is opaque to ultraviolet rays.

At this time, ultraviolet rays having a wavelength in the range of 200 nm to 500 nm can be generally used for irradiation, and it is desirable to appropriately select the wavelength via a filter or the like. Specific examples thereof include wavelengths of 248 nm, 254 nm, 303 nm, 313 nm, and 365 nm. Particularly preferably, it is 365 nm.

The surface energy of the image-forming underlayer film used in the present invention is gradually increased by irradiation with ultraviolet rays, and is saturated with a sufficient irradiation amount. This increase in surface energy results in a decrease in the contact angle of the image forming liquid, and as a result, the wettability of the image forming liquid in the ultraviolet irradiation portion is improved.

Therefore, when the image forming liquid is applied on the image forming lower layer film after UV irradiation, the image forming liquid self-organizes along the pattern shape drawn as the difference in surface energy on the image forming lower layer film. It is possible to obtain an electrode having an arbitrary pattern shape.

Therefore, it is necessary to irradiate the lower layer film for image formation with an amount of ultraviolet rays that sufficiently changes the contact angle of the image forming liquid, but from the viewpoint of energy efficiency and shortening of the manufacturing process, it is 40 J / cm ² or less. It is preferably 20 J / cm ² or less, more preferably 10 J / cm ² or less, and most preferably 10 J / cm 2 or less.

In addition, the larger the difference in the contact angle of the image forming liquid between the ultraviolet irradiated part and the unirradiated part of the image forming lower layer film, the easier the patterning becomes, and it is possible to process the electrode into a complicated pattern or a fine pattern shape. Become. When a solution having a low surface tension is used, the contact angle difference between the exposed portion and the unexposed portion is preferably 5 ° or more, more preferably 10 ° or more, and most preferably 20 ° or more. However, it is better to optimize appropriately in consideration of the method of applying the image forming liquid, the surface tension of the image forming liquid, the fineness of the image, and the flatness of the film.
For the same reason, the contact angle of the image forming liquid is preferably 15 ° or more in the UV-irradiated part, 10 ° or less in the UV-irradiated part, 20 ° or more in the UV-irradiated part, and UV irradiation. It is more preferably 10 ° or less in the portion, 30 ° or more in the ultraviolet-irradiated portion, and most preferably 5 ° or less in the ultraviolet-irradiated portion.

[Catalyst ink]
The catalyst ink for electroless plating used in the present invention is a catalyst ink containing (a) a dispersant, (b) metal fine particles, and (c) a solvent.
In particular, the catalyst ink of the present invention not only achieves thinning, but also suppresses the occurrence of disconnection in the obtained fine line pattern and improves straightness.
The catalyst ink of the present invention is suitably used as a material for forming a base layer for forming a metal plating film on a base material by electroless plating.

<(A) Dispersant>
Examples of the dispersant in the catalyst ink used in the present invention include polycarboxylic acid-based polymer dispersants such as polycarboxylic acid ammonium salt, polycarboxylic acid sodium salt, polycarboxylic acid triethylamine salt, and polycarboxylic acid triethanolamine salt; polyoxy. Block copolymer type polymer dispersant having a hydroxyl group such as ethylene alkyl ether carboxylate and alkyl hydroxy ether carboxylate; acrylic acid-maleic acid copolymer, styrene-maleic acid copolymer, acrylic acid-sulfonic acid A block copolymer type polymer dispersant having a carboxyl group such as a copolymer; a hyperbranched polymer having an ammonium group at the molecular end can be used. The dispersant can be used alone or in combination of two or more.

Among them, as the dispersant in the catalyst ink used in the present invention, (a) a hyperbranched polymer having an ammonium group at the molecular end and a weight average molecular weight of 1,000 to 5,000,000 is preferable.

前記式［１］中、Ｒ^１は、それぞれ独立して水素原子又はメチル基を表す。
また、Ｒ^２乃至Ｒ^４は、それぞれ独立して、水素原子、炭素原子数１乃至２０の直鎖状、枝分かれ状又は環状のアルキル基、炭素原子数７乃至２０のアリールアルキル基、又は－（ＣＨ_２ＣＨ_２Ｏ）_ｍＲ^５（式中、Ｒ^５は水素原子又はメチル基を表し、ｍは２乃至１００の任意の整数を表す。）を表す。上記アルキル基及びアリールアルキル基は、アルコキシ基、ヒドロキシ基、アンモニウム基、カルボキシ基又はシアノ基で置換されていてもよい。また、Ｒ^２乃至Ｒ^４のうちの２つの基が一緒になって、直鎖状、枝分かれ状又は環状のアルキレン基を表すか、又はＲ^２乃至Ｒ^４並びにそれらが結合する窒素原子が一緒になって環を形成してもよい。
またＸ^－は陰イオンを表し、ｎは繰り返し単位構造の数であって、５乃至１００，０００の整数を表す。<Hyperbranched polymer with ammonium group at the end>
The hyperbranched polymer used in the catalyst ink of the present invention is a polymer having an ammonium group at the molecular end and having a weight average molecular weight of 1,000 to 5,000,000, specifically, the following formula [1]. Examples include hyperbranched polymers represented by.

In the above formula [1], R ¹ independently represents a hydrogen atom or a methyl group.
Further, R ² to R ⁴ are independently hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, or-(. CH ₂ CH ₂ O) _m R ⁵ (in the formula, R ⁵ represents a hydrogen atom or a methyl group, and m represents an arbitrary integer of 2 to 100). The above alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxy group or a cyano group. Also, two groups of R ² to R ⁴ together represent a linear, branched or cyclic alkylene group, or R ² to R ⁴ and the nitrogen atom to which they bind together. May form a ring.
Further, X ^- represents an anion, n is the number of repeating unit structures, and represents an integer of 5 to 100,000.

Examples of the linear alkyl group having 1 to 20 carbon atoms in R ² to R ⁴ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group and n. -Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n -Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like can be mentioned, and a group having 8 or more carbon atoms is preferable because the catalyst ink of the present invention is difficult to elute into the electroless plating solution. Particularly, the n-octyl group is preferable. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like. Examples of the cyclic alkyl group include a cyclopentyl ring, a group having a cyclohexyl ring structure, and the like.
Examples of the arylalkyl group having 7 to 20 carbon atoms in R ² to R ⁴ include a benzyl group and a phenethyl group.
Further, examples of the linear alkylene group in which two groups of R ² to R ⁴ are combined include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group and the like. Be done. Examples of the branched alkylene group include an isopropylene group, an isobutylene group, and a 2-methylpropylene group. Examples of the cyclic alkylene group include alicyclic aliphatic groups having a cyclic structure having a monocyclic, polycyclic, or crosslinked cyclic structure having 3 to 30 carbon atoms. Specifically, a group having a monocyclo, bicyclo, tricyclo, tetracyclo, pentacyclo structure and the like having 4 or more carbon atoms can be mentioned. These alkylene groups may contain a nitrogen atom, a sulfur atom or an oxygen atom in the group.
The ring formed by ^R2 to ^R4 and the nitrogen atom bonded to them together in the structure represented by the formula [1] may contain a nitrogen atom, a sulfur atom or an oxygen atom in the ring. Frequently, for example, a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, a bipyridyl ring and the like can be mentioned.
Examples of the combination of R ² to R ⁴ include [methyl group, methyl group, methyl group], [methyl group, methyl group, ethyl group], [methyl group, methyl group, n-butyl group], and [methyl group]. Group, Methyl group, n-hexyl group], [Methyl group, Methyl group, n-octyl group], [Methyl group, Methyl group, n-decyl group], [Methyl group, Methyl group, n-dodecyl group], [Methyl group, methyl group, n-tetradecyl group], [methyl group, methyl group, n-hexadecyl group], [methyl group, methyl group, n-octadecyl group], [ethyl group, ethyl group, ethyl group], [N-butyl group, n-butyl group, n-butyl group], [n-hexyl group, n-hexyl group, n-hexyl group], [n-octyl group, n-octyl group, n-octyl group] Etc., and among them, a combination of [methyl group, methyl group, n-octyl group], [n-octyl group, n-octyl group, n-octyl group] is preferable.
Further, examples of the X ^- anion are preferably a halide ion, PF _6- ^, BF _4- ^or perfluoroalkane sulfonate.

上記式［２］中、Ａ^２はエーテル結合又はエステル結合を含んでいてもよい炭素原子数１乃至３０の直鎖状、枝分かれ状又は環状のアルキレン基を表す。
Ｙ^１乃至Ｙ^４は、それぞれ独立して、水素原子、炭素原子数１乃至２０のアルキル基、炭素原子数１乃至２０のアルコキシ基、ニトロ基、ヒドロキシ基、アミノ基、カルボキシ基又はシアノ基を表す。In the above formula [1], A ¹ represents a structure represented by the following formula [2].

In the above formula [2], A ² represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
Y ¹ to Y ⁴ independently have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxy group or a cyano group. show.

Specific examples of the alkylene group of A ² include a linear alkylene group such as a methylene group, an ethylene group, an n-propylene group, an n-butylene group and an n-hexylene group, an isopropylene group, an isobutylene group and 2-methyl. Examples thereof include a branched alkylene group such as a propylene group. Examples of the cyclic alkylene group include alicyclic aliphatic groups having a cyclic structure having a monocyclic, polycyclic or crosslinked cyclic structure having 3 to 30 carbon atoms. Specifically, a group having a monocyclo, bicyclo, tricyclo, tetracyclo, pentacyclo structure and the like having 4 or more carbon atoms can be mentioned. For example, structural examples (a) to (s) of the alicyclic portion of the alicyclic aliphatic group are shown below.

Examples of the alkyl group having ¹ to 20 carbon atoms of Y1 to Y4 in the above formula [ ² ] include a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, an n-pentyl group and the like. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an isopropoxy group, a cyclohexyloxy group, an n-pentyloxy group and the like. As Y1 to ^Y4 , a hydrogen atom or an alkyl group having ¹ to 20 carbon atoms is preferable.

It is preferable that A ¹ has a structure represented by the following formula [4].

前記式［３］中、Ｒ^１、Ｒ^２乃至Ｒ^４及びｎは上記と同じ意味を表す。Preferably, the hyperbranched polymer used in the present invention includes a hyperbranched polymer represented by the following formula [3].

In the above formula [3], R ¹ , R ² to R ⁴ and n have the same meanings as described above.

The hyperbranched polymer having the ammonium group at the molecular end used in the present invention can be obtained, for example, by reacting an amine compound with the hyperbranched polymer having a halogen atom at the molecular end.
The hyperbranched polymer having a halogen atom at the molecular end can be produced from the hyperbranched polymer having a dithiocarbamate group at the molecular end in accordance with the description of International Publication No. 2008/029688. As the hyperbranched polymer having the dithiocarbamate group at the molecular end, a commercially available product can be used, and Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd. can be preferably used.

The amine compounds that can be used in this reaction include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, and n as primary amines. -Hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine , N-Hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosylamine and other aliphatic amines; cyclopentylamine, cyclohexylamine and other alicyclic amines; benzylamine, phenethylamine and the like. Aralkylamines; aniline, pn-butylaniline, p-tert-butylaniline, pn-octylaniline, pn-decylaniline, pn-dodecylaniline, pn-tetradecylaniline, etc. Aniline, naphthylamines such as 1-naphthylamine and 2-naphthylamine, aminoanthracenes such as 1-aminoanthracene and 2-aminoanthracene, aminoanthraquinones such as 1-aminoanthraquinone, 4-aminobiphenyl, 2-aminobiphenyl and the like. Aminobiphenyls, 2-aminofluorene, 1-amino-9-fluorenone, 4-amino-9-fluorenone and other aminofluorenes, 5-aminoindane and other aminoindans, 5-aminoisoquinolin and other aminoisoquinolins. , 9-Aromatic amines such as aminophenanthrenes such as aminophenanthrene. Furthermore, N- (tert-butoxycarbonyl) -1,2-ethylenediamine, N- (tert-butoxycarbonyl) -1,3-propylenediamine, N- (tert-butoxycarbonyl) -1,4-butylenediamine, N -(Tart-butoxycarbonyl) -1,5-pentamethylenediamine, N- (tert-butoxycarbonyl) -1,6-hexamethylenediamine, N- (2-hydroxyethyl) amine, N- (3-hydroxypropyl) ) Amine, N- (2-methoxyethyl) amine, N- (2-ethoxyethyl) amine and other amine compounds can be mentioned.

Secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-n-pentylamine, ethylmethylamine, and methyl-. n-propylamine, methyl-n-butylamine, methyl-n-pentylamine, methyl-n-octylamine, methyl-n-decylamine, methyl-n-dodecylamine, methyl-n-tetradecylamine, methyl-n- Hexadecylamine, methyl-n-octadecylamine, ethylisopropylamine, ethyl-n-butylamine, ethyl-n-pentylamine, ethyl-n-octylamine, di-n-hexylamine, di-n-octylamine, di Alicyclic amines such as -n-dodecylamine, di-n-hexadecylamine, di-n-octadecylamine; alicyclic amines such as dicyclohexylamine; aralkylamines such as dibenzylamine; aromatic amines such as diphenylamine; Examples thereof include nitrogen-containing heterocyclic compounds such as phthalimide, pyrrole, piperidine, piperazine and imidazole. Further, bis (2-hydroxyethyl) amine, bis (3-hydroxypropyl) amine, bis (2-ethoxyethyl) amine, bis (2-propoxyethyl) amine and the like can be mentioned.

Examples of tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-octylamine, and tri-n-dodecyl. Amine, dimethylethylamine, dimethyl-n-butylamine, dimethyl-n-hexylamine, dimethyl-n-octylamine, dimethyl-n-decylamine, diethyl-n-decylamine, dimethyl-n-dodecylamine, dimethyl-n-tetradecyl Adipose amines such as amines, dimethyl-n-hexadecylamines, dimethyl-n-octadecylamines, dimethyl-n-eicosylamines; pyridine, pyrazine, pyrimidine, quinoline, 1-methylimidazole, 4,4'-bipyridyl, Examples thereof include nitrogen-containing heterocyclic compounds such as 4-methyl-4,4'-bipyridyl.

The amount of the amine compound that can be used in these reactions is 0.1 to 20 molar equivalents, preferably 0.5 to 10 molar equivalents, with respect to 1 mol of the halogen atom of the hyperbranched polymer having a halogen atom at the molecular terminal. It may be preferably 1 to 5 molar equivalents.

The reaction between the hyperbranched polymer having a halogen atom at the end of the molecule and the amine compound can be carried out in water or an organic solvent in the presence or absence of a base. The solvent used is preferably one capable of dissolving a hyperbranched polymer having a halogen atom at the molecular terminal and an amine compound. Further, a hyperbranched polymer having a halogen atom at the molecular terminal and an amine compound can be dissolved, but a solvent that does not dissolve the hyperbranched polymer having an ammonium group at the molecular terminal is more preferable because isolation is easy.
The solvent that can be used in this reaction may be any solvent as long as it does not significantly inhibit the progress of this reaction. Water; alcohols such as isopropanol; organic acids such as acetic acid; benzene, toluene, xylene, ethylbenzene, 1,2-di Aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran (THF) and diethyl ether; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and cyclohexanone; chloroform, dichloromethane, 1,2-dichloroethane Halogens such as; aliphatic hydrocarbons such as n-hexane, n-heptane, cyclohexane; N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP) and the like. Amids can be used. One of these solvents may be used, or two or more of these solvents may be mixed and used. The amount used is 0.2 to 1,000 times by mass, preferably 1 to 500 times by mass, more preferably 5 to 100 times by mass, most preferably 5 times by mass with respect to the mass of the hyperbranched polymer having a halogen atom at the molecular terminal. It is preferable to use a solvent having a mass of 5 to 50 times.

Suitable bases are generally alkali metal hydroxides and alkaline earth metal hydroxides (eg sodium hydroxide, potassium hydroxide, calcium hydroxide), alkali metal oxides and alkaline earth metal oxides (eg lithium oxide). , Calcium oxide), alkali metal hydrides and alkaline earth metal hydrides (eg sodium hydride, potassium hydride, calcium hydride), alkali metal amides (eg sodium amides), alkali metal carbonates and alkaline earth metal carbonates. Inorganic compounds such as salts (eg lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate), alkali metal bicarbonates (eg sodium bicarbonate), as well as alkali metal alkyls, alkyl magnesium halides, alkali metal alkoxides, alkaline earth metals. Organic metal compounds such as alkoxides and dimethoxymagnesiums are used. Particularly preferred are potassium carbonate and sodium carbonate. The amount used is 0.2 to 10 molar equivalents, preferably 0.5 to 10 molar equivalents, most preferably 1 to 5 molar equivalents, relative to 1 mol of the halogen atom of the hyperbranched polymer having a halogen atom at the end of the molecule. It is preferable to use the base of.

In this reaction, it is preferable to sufficiently remove oxygen in the reaction system before the start of the reaction, and it is preferable to replace the inside of the system with an inert gas such as nitrogen or argon. The reaction conditions are appropriately selected from 0.01 to 100 hours for the reaction time and 0 to 300 ° C. for the reaction temperature. The reaction time is preferably 0.1 to 72 hours and the reaction temperature is 20 to 150 ° C.

When a tertiary amine is used, a hyperbranched polymer represented by the formula [1] can be obtained regardless of the presence / absence of a base.
When a primary amine or a secondary amine compound is reacted with a hyperbranched polymer having a halogen atom at the molecular terminal in the absence of a base, the corresponding hyperbranched polymer has a terminal secondary amine and a third. An ammonium group-terminated hyperbranched polymer obtained by protonating a secondary amine is obtained. In addition, even when the reaction is carried out using a base, the terminal secondary amine of the corresponding hyperbranched polymer can be mixed with an aqueous solution of an acid such as hydrogen chloride, hydrogen bromide, or hydrogen iodide in an organic solvent. And an ammonium group-terminated hyperbranched polymer in which a tertiary amine is protonated is obtained.

The hyperbranched polymer has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography of 1,000 to 5,000,000, preferably 1,000 to 500,000, and more preferably 2. It is 000 to 200,000, most preferably 3,000 to 100,000. The dispersity Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, preferably 1.1 to 6.0, and more preferably 1.2 to 5. It is 0.

<(B) Metal fine particles>
The metal fine particles used in the catalyst ink of the present invention are not particularly limited, and the metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), and silver (Ag). , Tin (Sn), Platinum (Pt) and Gold (Au), and may be one kind of these metals or two or more kinds of alloys. Among them, palladium fine particles are mentioned as preferable metal fine particles. The metal oxide may be used as the metal fine particles.

The metal fine particles are obtained by reducing metal ions by, for example, a method of irradiating an aqueous solution of a metal salt with light using a high-pressure mercury lamp, a method of adding a compound having a reducing action (so-called reducing agent) to the aqueous solution, or the like. For example, the metal ion is reduced by adding an aqueous solution of a metal salt to the solution in which the hyperbranched polymer is dissolved and irradiating the solution with ultraviolet rays, or by adding an aqueous solution of the metal salt and a reducing agent to the solution. Thereby, the catalyst ink containing the hyperbranched polymer, the metal fine particles, and other components described later can be prepared while forming a complex of the hyperbranched polymer and the metal fine particles.

Examples of the metal salt include gold chloride acid, silver nitrate, copper sulfate, copper nitrate, copper acetate, tin chloride, first platinum chloride, platinum chloride acid, Pt (dba) ₂ [dba = dibenzylidene acetone], Pt (cod). ₂ [cod = 1,5-cyclooctadien], Pt (CH ₃ ) ₂ (cod), palladium chloride, palladium acetate (Pd (OC (= O) CH ₃ ) ₂ ), palladium nitrate, Pd ₂ (dba) _3. CHCl ₃ , Pd (dba) ₂ , rhodium chloride, rhodium acetate, ruthenium chloride, ruthenium acetate, Ru (cod) (cot) [cot = cyclooctatriene], iridium chloride, iridium acetate, Ni (cod) ₂ , etc. Can be mentioned.
The reducing agent is not particularly limited, and various reducing agents can be used, and it is preferable to select the reducing agent according to the metal species and the like contained in the obtained catalyst ink. Examples of the reducing agent that can be used include boron hydride metal salts such as sodium boron hydride and potassium boron hydride; aluminum lithium hydride, potassium aluminum hydride, cesium hydride, aluminum beryllium hydride, and hydrogenation. Hydrogenated aluminum salts such as aluminum magnesium and hydrogenated aluminum calcium; hydrazine compounds; citric acid and its salts; succinic acid and its salts; ascorbic acid and its salts; primary or secondary such as methanol, ethanol, isopropanol and polyols. Secondary alcohols; Tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], ethylenediaminetetraacetic acid [EDTA]; hydroxylamine; tri-n-propylphosphine, tri-n- Butylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis (diphenylphosphino) ethane [DPPE], 1,3-bis (diphenylphosphino) propane [DPPP], 1 , 1'-bis (diphenylphosphino) ferrocene [DPPF], 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl [BINAP] and the like.

The average particle size of the metal fine particles is preferably 1 to 100 nm. The reason is that when the average particle size of the metal fine particles exceeds 100 nm, the surface area decreases and the catalytic activity decreases. The average particle size is more preferably 75 nm or less, and particularly preferably 1 to 30 nm.

The amount of the (a) hyperbranched polymer added to the catalyst ink used in the present invention is preferably 50 to 2,000 parts by mass with respect to 100 parts by mass of the (b) metal fine particles. If it is less than 50 parts by mass, the dispersibility of the metal fine particles is insufficient, and if it exceeds 2,000 parts by mass, the organic matter content increases and problems with physical properties are likely to occur. More preferably, it is 100 to 1,000 parts by mass.

[Complex]
In the catalyst ink used in the present invention, it is preferable that the dispersant and the metal fine particles form a complex.
Here, the complex means that due to the action of the ammonium group or the hydroxy group at the end of the dispersant, both coexist in contact with or in close contact with the metal fine particles to form a particulate form. In other words, the complex is described above. It is expressed as a complex having a structure in which an ammonium group or a hydroxy group of a dispersant is attached or coordinated to metal fine particles.
Therefore, in the "complex" in the present invention, not only the metal fine particles and the dispersant are bonded to form one complex as described above, but also the metal fine particles and the dispersant form a bonded portion. It may also include those that exist independently without each other.

The complex of the dispersant and the metal fine particles may be formed in advance by combining the dispersant and the metal fine particles, or may be carried out at the same time as the preparation of the catalyst ink. The method includes synthesizing metal fine particles stabilized to some extent with a lower ammonium ligand and then exchanging the ligand with a dispersant, or directly reducing metal ions in a solution of the dispersant to form a complex. There is a way to form.

In the ligand exchange method, metal fine particles stabilized to some extent by a lower ammonium ligand as a raw material can be synthesized by the method described in Journal of Organometallic Chemistry 1996, 520, 143-162 and the like. The desired metal fine particle composite can be obtained by dissolving the dispersant in the reaction mixed solution of the obtained metal fine particles and stirring at room temperature (about 25 ° C.) or heating.
The solvent used is not particularly limited as long as it can dissolve the metal fine particles and the dispersant in a concentration higher than the required concentration, but specifically, alcohols such as ethanol, n-propanol and isopropanol; methylene chloride and chloroform. Halogenated hydrocarbons such as: Tetrahydrofuran (THF), 2-methyltetrahydrofuran, cyclic ethers such as tetrahydropyran; nitriles such as acetonitrile and butyronitrile and a mixture of these solvents are preferable. Can be mentioned.
The temperature at which the reaction mixture of the metal fine particles and the dispersant are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent, and is preferably in the range of room temperature (about 25 ° C.) to 60 ° C.
In the ligand exchange method, the metal fine particles can be stabilized to some extent in advance by using a phosphine-based dispersant (phosphine ligand) in addition to the amine-based dispersant (lower ammonium ligand).

As a direct reduction method, a metal ion and a dispersant are dissolved in a solvent and reduced with primary or secondary alcohols such as methanol, ethanol, isopropanol and polyol to obtain a desired metal fine particle composite. be able to.
As the metal ion source used here, the above-mentioned metal salt can be used.
The solvent to be used is not particularly limited as long as it can dissolve the metal ion and the dispersant in a concentration higher than the required concentration, but specifically, alcohols such as methanol, ethanol, propanol and isopropanol; methylene chloride, chloroform and the like. Halogenized hydrocarbons; Cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrogen, tetrahydropyran; nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide (DMF), N-methyl-2-pyrrolidone. Examples thereof include amides such as (NMP); sulfoxides such as dimethyl sulfoxide and a mixed solution of these solvents, preferably alcohols, halogenated hydrocarbons, cyclic ethers, and more preferably ethanol. , Isopropanol, chloroform, tetrahydrofuran and the like.
The temperature of the reduction reaction can usually be in the range of 0 ° C. to the boiling point of the solvent, preferably in the range of room temperature (approximately 25 ° C.) to 60 ° C.

As another direct reduction method, the desired metal fine particle composite can be obtained by dissolving the metal ion and the dispersant in a solvent and reacting them in a hydrogen gas atmosphere.
The metal ion source used here includes the above-mentioned metal salt, hexacarbonylchrome [Cr (CO) ₆ ], pentacarbonyl iron [Fe (CO) ₅ ], and octacarbonyl dicobalt [Co ₂ (CO) ₈ ]. , Tetracarbonyl nickel [Ni (CO) ₄ ] and other metal carbonyl complexes can be used. Further, 0-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes can also be used.
The solvent used is not particularly limited as long as it can dissolve metal ions and a dispersant in a concentration higher than the required concentration, but specifically, alcohols such as ethanol and propanol; halogenated carbonized such as methylene chloride and chloroform. Hydrogens; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile and butyronitrile and a mixed solution of these solvents can be mentioned, with preference given to tetrahydrofuran.
The temperature at which the metal ion and the dispersant are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent.

Further, as a direct reduction method, a target metal fine particle composite can be obtained by dissolving a metal ion and a dispersant in a solvent and causing a thermal decomposition reaction.
As the metal ion source used here, the above-mentioned metal salt, metal carbonyl complex, other zero-valent metal complex, and metal oxide such as silver oxide can be used.
The solvent to be used is not particularly limited as long as it can dissolve the metal ion and the dispersant in a concentration higher than the required concentration, but specifically, alcohols such as methanol, ethanol, n-propanol, isopropanol and ethylene glycol; Halogenized hydrocarbons such as methylene chloride and chloroform; Cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrogen and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; Aromatic hydrocarbons such as benzene and toluene and Examples thereof include a mixed solution of these solvents, preferably toluene.
The temperature at which the metal ion and the dispersant are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent, preferably near the boiling point of the solvent, for example, 110 ° C. (heat reflux) in the case of toluene.

The complex of the dispersant and the metal fine particles thus obtained can be in the form of a solid substance such as powder through a purification treatment such as reprecipitation.

<Solvent>
The solvent used for the catalyst ink used in the present invention is particularly limited as long as it can dissolve or disperse the above complex (for example, a hyperbranched polymer having an ammonium group and metal fine particles) and stably eject it by inkjet. Although not, it is desirable to include monoalcohol. Further, by using a mixed solvent with a polyhydric alcohol in order to prevent drying and adjust the viscosity, it becomes possible to stably eject the inkjet.

[Mono alcohol]
Examples of monoalcohols include lower alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, sec-butanol, and tert-butanol; ethylene glycol monomethyl ether (methyl cellosolve) and ethylene glycol monoethyl. Ethylene glycol monoalkyl ethers (cellosolves) such as ether (ethyl cellosolve), ethylene glycol monopropyl ether (propyl cellosolve), ethylene glycol monoisopropyl ether (isopropyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve); propylene glycol monomethyl ether (PGME), propylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; 3-methoxypropanol, 3-ethoxypropanol, 3-propoxypropanol, 3-butoxypropanol, 3 -Other alkoxy alcohols such as methoxybutanol, 3-methoxy-3-methylbutanol, 4-methoxybutanol; diacetone alcohols; lactic acid esters such as methyl lactate and ethyl lactate. These monoalcohols may be used alone or in combination of two or more.
Among these, lower alcohols, alkoxy alcohols and diacetone alcohols are preferable, and 1-propanol, butyl cellosolve and diacetone alcohol are more preferable.

[Multivalent alcohol]
Examples of the polyhydric alcohol include ethylene glycol; propanediols such as 1,2-propanediol (propylene glycol), 1,3-propanediol, and 2-methyl-1,3-propanediol; 1,2-butanediol. Butanediols such as diol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,4-butanediol; 1,5-pentanediol, 3-methyl- Pentandiols such as 1,5-pentanediol and 2-methyl-2,4-pentanediol; hexanediols such as 1,6-hexanediol; triols such as glycerin and 1,2,6-hexanetriol and the like. Can be mentioned. These polyhydric alcohols may be used alone or in combination of two or more.
Among these, propanediols and butanediols are preferable, and 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,3-butanediol and 1,4-butanediol are more preferable.

In addition, a good solvent may be added to improve the solubility. Examples of such a good solvent include aprotic polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone.

The blending amount of the mixed solvent (c) in the catalyst ink used in the present invention is such that the concentration of the composite is 0.05 to 10% by mass, preferably 0.1 to 5% by mass. Is preferable.
If the concentration of the composite is less than 0.05% by mass, disconnection may easily occur when the catalyst ink is applied by inkjet, and if the concentration of the composite exceeds 10% by mass, the inkjet nozzle is clogged. May occur.

<Polymerizable compound having one or more (meth) acryloyl groups in the molecule>
When it is desired to cure the catalytic ink used in the present invention with light, it is preferable to contain a polymerizable compound having one or more (meth) acryloyl groups in the molecule. The polymerizable compound having a (meth) acryloyl group is a compound having a (meth) acryloyl group and having at least one structure selected from the group consisting of an oxyalkylene structure, a urethane structure and a poly (meth) acrylic structure. It is preferable that the compound has a (meth) acryloyl group and has at least one structure selected from the group consisting of an oxyalkylene structure and a urethane structure. In particular, a compound having a (meth) acryloyl group and having an oxyalkylene structure, a urethane (meth) acrylate compound, or a poly (meth) acrylic compound having a (meth) acryloyl group is preferable. Further, the polymerizable compound having a (meth) acryloyl group preferably has two or more (meth) acryloyl groups in the molecule.
Examples of the oxyalkylene structure include a structure having an oxyalkylene group. As the oxyalkylene group, an oxyalkylene group having 2 to 4 carbon atoms is preferable, and an oxyethylene group [-OCH ₂ CH _2-- ". ] Or an oxypropylene group [-OCH ₂ C (CH ₃ ) H-] is preferable. The oxyalkylene group may be a poly (oxyalkylene) group in which a plurality of the oxyalkylene groups are linked, and in that case, one kind of oxyalkylene group may be contained alone, or two or more kinds may be possessed in combination. May be good. When having a plurality of kinds of oxyalkylene groups, the bond thereof may be either a block bond or a random bond.
In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

<Meta) A compound having one acryloyl group and having an oxyalkylene structure>
Examples of such compounds include the organic compounds shown in (1) to (5) below.

(1) Monofunctional (having one (meth) acryloyl group) compound (meth) A compound having one acryloyl group and having an oxyalkylene structure includes, for example, 2-phenoxyethyl (meth) acrylate and ethylene oxide modification. o-phenylphenol (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) Acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol mono (2-ethylhexyl) ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) Acrylate, tetraethylene glycol monolauryl ether (meth) acrylate, tetraethylene glycol mono (nonylphenyl) ether (meth) acrylate, octaethylene glycol mono (meth) acrylate, nonaethylene glycol monomethyl ether (meth) acrylate, decaethylene glycol mono (Meta) acrylate, tridecaethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (meth) Acrylate, tetrapropylene glycol mono (meth) acrylate, pentapropylene glycol mono (nonylphenyl) ether (meth) acrylate, hexapropylene glycol mono (meth) acrylate, nonapropylene glycol mono (meth) acrylate, tridecapropylene glycol mono (meth) ) Acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate and the like can be mentioned.

(2) Bifunctional (with two (meth) acryloyl groups) compound (meth) A compound having two acryloyl groups and having an oxyalkylene structure includes, for example, diethylene glycol di (meth) acrylate and triethylene glycol di. (Meta) acrylate, tetraethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, heptapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tri (tetramethylene glycol) di (meth) acrylate, nona (tetra) Methylene glycol) di (meth) acrylate, poly (tetramethylene glycol) di (meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate ], Propylene oxide-modified bisphenol A di (meth) acrylate [propylene oxide added moles 2 to 30], ethylene oxide-propylene oxide modified bisphenol A di (meth) acrylate, 9,9-bis (4- (2-((meth) ) Acryloyloxy) ethoxy) phenyl) fluorene and the like.

(3) Trifunctional (having three (meth) acryloyl groups) compound (meth) A compound having three acryloyl groups and having an oxyalkylene structure includes, for example, ethylene oxide-modified 1,1,1-trimethylolethane. Tri (meth) acrylate [ethylene oxide-added moles 3 to 30], ethylene oxide-modified trimethylolpropane tri (meth) acrylate [ethylene oxide-added moles 3 to 30], propylene oxide-modified trimethylolpropane tri (meth) acrylate [propylene oxide addition Number of moles 3 to 30], ethylene oxide-modified glycerintri (meth) acrylate [number of moles added with ethylene oxide 3 to 30], propylene oxide-modified glycerintri (meth) acrylate [number of moles added with propylene oxide 3 to 30], Tris (2-( Acryloyloxy) ethyl) isocyanurate, ε-caprolactone-modified tris (2- (acryloyloxy) ethyl) isocyanurate [ε-caprolactone-added moles 1 to 30] and the like can be mentioned.

(4) A tetrafunctional (with four (meth) acryloyl groups) compound (meth) As a compound having four acryloyl groups and having an oxyalkylene structure, for example, ethylene oxide-modified ditrimethylolpropane tetra (meth) acrylate [ Ethylene oxide addition moles 4 to 40], ethylene oxide-modified pentaerythritol tetra (meth) acrylate [ethylene oxide addition moles 4 to 40] and the like can be mentioned.

(5) Compounds having five or more functionalities (having five or more (meth) acryloyl groups) Examples of compounds having five or more (meth) acryloyl groups and an oxyalkylene structure include ethylene oxide-modified dipentaerythritol hexa (). Examples thereof include meth) acrylate [ethylene oxide-added moles 6 to 60], ethylene oxide-modified trypentaerythritol octa (meth) acrylate [ethylene oxide-added moles 6 to 60], and the like.

<Urethane (meth) acrylate compound>
Examples of such compounds include the organic compounds shown in (1) to (6) below.

(1) Monofunctional (having one (meth) acryloyl group) urethane (meth) acrylate A compound having one (meth) acryloyl group and having a urethane structure is not particularly limited, but is not particularly limited, and is, for example, polyisocyanate. Isocyanate component) and monool (active hydrogen component) are reacted to obtain an isocyanate-terminated prepolymer, which is reacted with a (meth) acryloyl group and a compound having an isocyanate-reactive group to form a (meth) acryloyl group. A urethane (meth) acrylate having an average of 1 per molecule can be obtained. Polyols may be used instead of monools, but in that case it is necessary to operate so that (meth) acryloyloxy groups are not introduced into some of the terminal hydroxy groups of the polyols.

(2) Bifunctional (having two (meth) acryloyl groups) Urethane (meth) acrylate As a compound having two (meth) acryloyl groups and having a urethane structure, for example, (meth) acrylic of phenylglycidyl ether. Examples thereof include urethanes of an acid adduct and hexamethylene diisocyanate, and urethanes of a (meth) acrylic acid adduct of phenylglycidyl ether and toluene diisocyanate.

Commercially available products can be preferably used as the above bifunctional urethane (meth) acrylate, for example, AH-600, AT-600 [all of which are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-2PPA, U-200PA. , UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P, UA-W2A [all manufactured by Shin Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 210, 215, 230, 244, 245, 270, 280/15IB, 284, 285, 4858, 8307, 8402, 8411, 8804, 8807, 9227EA, same 9270, KRM (registered trademark) 7735 [all manufactured by Daicel Ornex Co., Ltd.]; Shikou (registered trademark) UV-6630B, 7000B, 7461TE, 2000B, 2750B, 3000, 3200B, same 3210EA, 3300B, 3310B, 3500BA, 3520TL, 3700B, 6640B [all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] and the like.

(3) Trifunctional (having three (meth) acryloyl groups) Urethane (meth) acrylate As a commercially available product of a compound having three (meth) acryloyl groups and having a urethane structure, for example, NK Oligo UA-7100 [Manufactured by Shin Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 204, 205, 264, 265, 294 / 25HD, 1259, 4820, 8311, 8465, 8701, 9260, KRM (registered trademark) 8296, 8667 [all manufactured by Daicel Ornex Co., Ltd.]; Shikou (registered trademark) UV-7550B, 7000B, 7510B, 7461TE, 2750B [all of which are Japanese synthetics. Made by Chemical Industry Co., Ltd.] and the like.

(4) As a commercially available product of a compound having four functional (meth) acryloyl groups (having four (meth) acryloyl groups) urethane (meth) acrylate (meth) acryloyl groups and having a urethane structure, for example, EBECRYL (registered trademark). 8210, 8405, KRM (registered trademark) 8528 [all manufactured by Daicel Ornex Co., Ltd.]; Shikou (registered trademark) UV-7650B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] and the like.

(5) Urethane (meth) acrylate having five or more functionalities (having five or more (meth) acryloyl groups) Examples of the compound having five or more (meth) acryloyl groups and having a urethane structure include pentaerythritol tri (). Urethanes of meta) acrylate and hexamethylene diisocyanate, urethanes of pentaerythritol tri (meth) acrylate and toluene diisocyanate, urethanes of pentaerythritol tri (meth) acrylate and isophorone diisocyanate, dipentaerythritol penta (meth) acrylate And a urethane product of hexamethylene diisocyanate and the like.

Commercially available products can be suitably used for the above-mentioned 5-functional or higher functional urethane (meth) acrylate, for example, UA-306H, UA-306T, UA-306I, UA-510H [all of which are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-6LPA, U-10HA, U-10PA, U-1100H, U-15HA, UA-53H, UA-33H [all manufactured by Shin Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 220, 1290, 5129, 8254, 8301R, KRM (registered trademark) 8200, 8200AE, 8904, 8452 [all manufactured by Daicel Ornex Co., Ltd.]; Registered trademarks) UV-1700B, 6300B, 7600B, 7605B, 7610B, 7620EA, 7630B, 7640B, 7650B [all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] and the like.

(6) Polyurethane (meth) acrylate As the polyurethane (meth) acrylate, a commercially available product can be preferably used. For example, Acryt 8BR-500, 8BR-600, 8BR-930M [all of which are manufactured by Taisei Fine Chemical Co., Ltd.]. ] Etc. Polyurethane (meth) acrylate having a urethane structure in the side chain; Acryt 8UH-1006, 8UH-1012 [all manufactured by Taisei Fine Chemical Co., Ltd.], etc. Polyurethane (meth) having a urethane structure in the main chain Examples include acrylate.

[Poly (meth) acrylic compound having (meth) acryloyl group]
The compound is not particularly limited as long as it is a (meth) acrylic polymer having a (meth) acryloyl group in the side chain. Such a polymer (also referred to as (meth) acrylic (meth) acrylate) is obtained, for example, by polymerizing a (meth) acrylic monomer containing a (meth) acrylate having a reactive group as a monomer component, and the polymer obtained by polymerizing the polymer. It is obtained by reacting a compound having a functional group capable of reacting with a reactive group and a (meth) acryloyl group.

As the (meth) acrylic (meth) acrylate, a commercially available product can be preferably used. For example, Acryt 8KX-077, 8KX-078, 8KX-078H, 8KX-127, 8KX-128, 8KX-012C. , 8KX-014C, 8KX-018C, 8KX-052C, 8KQ-2001 [all manufactured by Taisei Fine Chemical Co., Ltd.]; SMP-220A, SMP-250A, SMP-360A, SMP-550A [and above] , All manufactured by Kyoeisha Chemical Co., Ltd.] and the like.

The amount of the polymerizable compound having a (meth) acryloyl group added to the base material used in the present invention is 0.1 to 500 mass by mass with respect to 100 parts by mass of the composite formed of the hyperbranched polymer and the metal fine particles. Parts are preferable, and 1 to 200 parts by mass are more preferable.

<Photopolymerization initiator>
Known photopolymerization initiators can be used as the base material used in the present invention, and for example, alkylphenones, benzophenones, acylphosphine oxides, Michler's benzoylbenzoates, and oxime esters can be used. , Tetramethylthium monosulfides, thioxanthones and the like.
In particular, a photocleavable photoradical polymerization initiator is preferable. Examples of the photocleavable photoradical polymerization initiator are those described in the latest UV curing technology (page 159, publisher: Kazuhiro Takausu, publisher: Technical Information Association, 1991). ..
Examples of commercially available photoradical polymerization initiators include IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, and CGI1850. , CG24-61, TPO, OXE-01, OXE-02, Darocur (registered trademark) 1116, 1173 [above, manufactured by BASF Japan Ltd.], ESACURE KIP150, KIP65LT, KIP100F, KT37. , KT55, KTO46, KIP75 [above, manufactured by Lamberti] and the like. A plurality of types of these polymerization initiators can be used in combination.

The photopolymerization initiator may be used alone or in combination of two or more. The amount added is 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the (c) polymerizable compound.

<Binder resin>
The catalyst ink used in the present invention may contain a binder resin. By using the binder resin, the adhesion of the electroless plating base layer to the substrate can be strengthened.

As the binder resin, a resin that is dispersed or dissolved in the catalyst ink can be used. Specific examples of the binder resin include epoxy resin, polyester resin, acrylic resin, polyurethane resin, acrylic / silicon resin, acrylic / urethane resin, polyamide resin, polyimide resin, shellac resin, melamine resin, urea resin, and fluororesin. Be done. Among them, at least one selected from the group consisting of polyester resin, polyurethane resin, acrylic / silicon resin, acrylic / urethane resin, polyamide resin and polyimide resin is preferable.

The amount of the binder resin added to the catalyst ink used in the present invention is preferably 10 to 5000 parts by mass, more preferably 100 to 2000 parts by mass with respect to 100 parts by mass of the composite.

<Other additives>
Additives such as a surfactant and a thickener may be appropriately added to the catalyst ink used in the present invention as long as the effects of the present invention are not impaired.

Examples of the thickener include polyacrylic acids (including crosslinked ones) such as carboxyvinyl polymer (carbomer); polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and polystyrene (PS). ) And other vinyl polymers; polyethylene oxides; polyester; polycarbonate; polyamide; polyurethane; dextrin, agar, caraginan, alginic acid, arabic gum, guar gum, tragant gum, locust bean gum, starch, pectin, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose Polysaccharides such as; proteins such as gelatin and casein, etc. may be mentioned. In addition, each of the above polymers includes not only homopolymers but also copolymers. These thickeners may be used alone or in combination of two or more.
The catalyst ink used in the present invention can adjust the viscosity and rheological characteristics of the catalyst ink by adding a thickener as needed.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether and polyoxy. Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurates, sorbitan monopalmitates, sorbitan monostearates, sorbitan monooleates, sorbitan tristearates, Solbitan fatty acid esters such as sorbitan trioleate; polyoxyethyleneonion-based surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate. EFTop (registered trademark) EF-301, EF-303, EF-352 [above, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.], Megafuck (registered trademark) F-171, F-173, R -08, R-30 [above, manufactured by DIC Co., Ltd.], Novec (registered trademark) FC-430, FC-431 [above, manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard (registered trademark) AG-710 Examples thereof include fluorosurfactants such as [manufactured by Asahi Glass Co., Ltd.] and Surflon (registered trademark) S-382 [manufactured by AGC Seimi Chemical Co., Ltd.].

These additives may be used alone or in combination of two or more. The amount of the additive used is preferably 0.001 to 50 parts by mass, more preferably 0.005 to 10 parts by mass, and 0.01 with respect to 100 parts by mass of the composite formed of the dispersant and the metal fine particles. Up to 5 parts by mass is even more preferable.

[Electroless plating base layer]
The above-mentioned catalyst ink can be applied onto a substrate by an inkjet method to form a layer, whereby an electroless plating base layer can be formed. This electroless plating base layer is also an object of the present invention.

As a specific method for forming the electroless plating base layer from the catalyst ink containing the dispersant, the metal fine particles and the mixed solvent, first, the hyperbranched polymer, the metal fine particles (preferably a composite composed of these) and the surface adjustment are performed. The agent is dissolved or dispersed in the above-mentioned mixed solvent to prepare a catalytic ink in the form of a varnish. Then, the varnish is applied onto a substrate having a parent liquid portion and a liquid repellent portion for forming a metal plating film, and then the solvent is evaporated and dried to form a thin layer. The coating method at that time includes spin coating method; blade coating method; dip coating method; roll coating method; bar coating method; die coating method; spray coating method; inkjet method; fountain pen nanolithography (FPN), dip pen nanolithography. Pen lithography such as (DPN); letterpress printing methods such as typographic printing, flexo printing, resin letterpress printing, contact printing, microcontact printing (μCP), nanoimprinting lithography (NIL), nanotransfer printing (nTP); gravure printing. , Recessed printing method such as engraving; Flat plate printing method; Screen printing, stencil printing method such as copying plate; Offset printing method, etc. Among them, the inkjet method can efficiently form (draw) fine patterns. It is particularly preferable in that it can be produced and is extremely advantageous industrially.

The method for drying the solvent is not particularly limited, and for example, the solvent may be evaporated using a hot plate or an oven in an appropriate atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or in a vacuum. This makes it possible to obtain an underlayer having a uniform film formation surface. The firing temperature is not particularly limited as long as the solvent can be evaporated, but it is preferably 40 to 250 ° C.

[Electroless plating treatment, metal plating film, metal film base material]
By electroless plating the electroless plating base layer formed on the substrate obtained as described above, a metal plating film is formed on the electroless plating base layer. The metal plating film thus obtained, and the metal film base material provided on the base material in the order of the electroless plating base layer and the metal plating film are also the objects of the present invention.
The electroless plating treatment (process) is not particularly limited and can be performed by any generally known electroless plating treatment. For example, the plating is performed using a conventionally known electroless plating solution. A general method is to immerse the electroless plating base layer formed on the substrate in a liquid (bath).

The electroless plating solution mainly contains a metal ion (metal salt), a complexing agent, and a reducing agent, and is a pH adjuster, a pH buffer, and a reaction accelerator (second complexing agent) according to other uses. , Stabilizers, surfactants (for imparting gloss to the plating film, for improving the wettability of the surface to be treated, etc.) and the like are appropriately included.
Examples of the metal used for the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold and alloys thereof, which are appropriately selected according to the purpose. Will be done.
Further, the complexing agent and the reducing agent may be appropriately selected according to the metal ion.
As the electroless plating solution, a commercially available plating solution may be used. For example, an electroless nickel plating chemical (Melplate (registered trademark) NI series) manufactured by Meltex Co., Ltd. and an electroless copper plating chemical (Melplate (Melplate (registered trademark))). Registered trademark) CU series); Electrolytic nickel plating solution (ICP Nicolon (registered trademark) series) manufactured by Okuno Pharmaceutical Co., Ltd., Electrolytic copper plating solution (OPC-700 Electrolytic copper MK, ATS Adcopper IW) ), Electrolytic tin plating solution (Substar SN-5), Electrolytic gold plating solution (Flash Gold 330, Self Gold OTK-IT); Electrolytic palladium plating solution (Palette II) manufactured by Kojima Chemical Co., Ltd., Electrolytic gold plating solution (Dip G series, NC Gold series); Electrolytic silver plating solution manufactured by Sasaki Chemicals Co., Ltd. (Sdia AG-40); Electrolytic nickel plating solution manufactured by Nippon Kanizen Co., Ltd. (Shoomer (Shoomer (Shoomer)) Registered trademark) series, Schumaer (registered trademark) Crab black (registered trademark) series), Electrolytic palladium plating solution (S-KPD); Dow Chemical Co., Ltd. electroless copper plating solution (Cuposit (registered trademark) Coppermix series , Circuposit (registered trademark) series), Electrolytic palladium plating solution (Paramars (registered trademark) series), Electrolytic nickel plating solution (Duraposit (registered trademark) series), Electrolytic gold plating solution (Aurolectrolless (registered) Series), Electrolytic tin plating solution (Tinposit (registered trademark) series); Electrolytic copper plating solution manufactured by Uemura Kogyo Co., Ltd. (Sulcup (registered trademark) ELC-SP, PSY, PCY, PGT , PSR, PEA, PMK); a non-electrolytic copper plating solution (Print Gantt (registered trademark) PV) manufactured by Attec Japan Co., Ltd. can be preferably used.

In the electroplating-free plating step, the metal film forming speed is adjusted by adjusting the plating bath temperature, pH, immersion time, metal ion concentration, presence / absence of stirring and stirring speed, presence / absence of supply of air / oxygen, supply speed, and the like. And the film thickness can be controlled.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the examples, the physical properties of the sample were measured using the following devices under the following conditions.
(1) GPC (Gel Permeation Chromatography)
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Showa Denko Corporation Shodex® GPC KF-804L + GPC KF-803L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: UV (254 nm), RI
(2) ^{1 1} H NMR spectrum device: JNM-L400 manufactured by JEOL Ltd.
Solvent: CDCl ₃
Reference peak: Tetramethylsilane (0.00ppm)
(3) ¹³ C NMR spectrum device: JNM-ECA700 manufactured by JEOL Ltd.
Solvent: CDCl ₃
Relaxation reagent: Trisacetylacetonatochrome (Cr (acac) ₃ )
Reference peak: CDCl ₃ (77.0 ppm)
(4) ICP emission analysis (inductively coupled plasma emission analysis)
Equipment: ICPM-8500 manufactured by Shimadzu Corporation
(5) TEM (Transmission Electron Microscope) Imaging Device: H-8000 manufactured by Hitachi High-Technologies Corporation
(6) Inkjet system Equipment: Inkjet Designer manufactured by Cluster Technology Co., Ltd.
Driver: WaveBuilder (registered trademark) PIJD-1SET manufactured by Cluster Technology Co., Ltd.
Head: PulseInjector (registered trademark) PIJ-15NSET manufactured by Cluster Technology Co., Ltd. (nozzle diameter: 15 μm)
(7) UV irradiation device: US5-0401 manufactured by Eye Graphics Co., Ltd.

ＭＯＩ－ＤＥＭ：下記式（Ｄ１）で示されるカレンズＭＯＩ－ＤＥＭ［昭和電工（株）製］

ＰＡＧ１２１：式（Ｃ２）で表されるＩｒｇａｃｕｒｅ（登録商標）ＰＡＧ １２１［ＢＡＳＦジャパン（株）製］

ＰＧＭ－ＳＴ：１－メトキシ－２－プロパノール分散シリカゾル（日産化学工業（株）製）
ＰＭ－Ｐ：プロピレングリコールモノメチルエーテル
ＰＭＡ－Ｐ：プロピレングリコールモノメチルエーテルアセテート
ＨＰＳ：ハイパーブランチポリスチレン［日産化学工業（株）製 ハイパーテック（登録商標）ＨＰＳ－２００］
ＩＰＡ：イソプロパノール［関東化学（株）製］
ＩＰＥ：ジイソプロピルエーテル［純正化学（株）製］
８ＫＸ０７８Ｈ：アクリル（メタ）アクリレート［大成ファインケミカル（株）製 アクリット８ＫＸ－０７８Ｈ］
Ａ６００：ポリエチレングリコールジアクリレート［新中村化学工業（株）製 ＮＫエステルＡ６００］
ＯＸＥ０１：１，２‐オクタンジオン，１‐［４‐（フェニルチオ）‐，２‐（ｏ‐ベンゾイルオキシム）］［ＢＡＳＦジャパン（株）製 Ｉｒｇａｃｕｒｅ（登録商標）ＯＸＥ０１］
ＤＡＡ：ジアセトンアルコール［純正化学（株）製］
１，３ＢＧ：１，３-ブタンジオール［純正化学（株）製］
ＰｈＣ：フェニルセロソルブ［純正化学（株）製］The abbreviations used are as follows.
HPMA: 4-Hydroxyphenyl methacrylate PEGMA: Poly (ethylene glycol) methacrylate Average M _n 360 (manufactured by SIGMA-ALDRICH)
HEMA: 2-Hydroxyethyl methacrylate BMAA: N-butoxymethylacrylamide AIBN: α, α'-azobisisobutyronitrile FMAA: Compound represented by the following formula (A1)

MOI-DEM: Calends MOI-DEM represented by the following formula (D1) [manufactured by Showa Denko KK]

PAG 121: Irgure (registered trademark) PAG 121 represented by the formula (C2) [manufactured by BASF Japan Ltd.]

PGM-ST: 1-methoxy-2-propanol dispersed silica sol (manufactured by Nissan Chemical Industries, Ltd.)
PM-P: Propylene Glycol Monomethyl Ether PMA-P: Propylene Glycol Monomethyl Ether Acetate HPS: Hyperbranched Polystyrene [Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industry Co., Ltd.]
IPA: Isopropanol [manufactured by Kanto Chemical Co., Inc.]
IPE: Diisopropyl ether [manufactured by Junsei Chemical Co., Ltd.]
8KX078H: Acrylic (meth) acrylate [Acryt 8KX-078H manufactured by Taisei Fine Chemical Co., Ltd.]
A600: Polyethylene glycol diacrylate [NK ester A600 manufactured by Shin Nakamura Chemical Industry Co., Ltd.]
OXE01: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)] [Irgacure (registered trademark) OXE01 manufactured by BASF Japan Ltd.]
DAA: Diacetone alcohol [manufactured by Junsei Chemical Co., Ltd.]
1,3BG: 1,3-Butanediol [manufactured by Junsei Chemical Co., Ltd.]
PhC: Phenylcellosolve [manufactured by Junsei Chemical Co., Ltd.]

２００ｍｌの三つ口フラスコにＮ－ヒドロキシメチルアクリルアミド［１］（１０．０ｇ、９８．９１ｍｍоｌ）、３，３，４，４，５，５，６，６，６－ノナフルオロヘキサン－１－オール［２］（１３．１ｇ、４９．４６ｍｍоｌ）、リン酸（０．２４ｇ、２．４７ｍｍоｌ）、２，６－ジ－ターシャリー－ブチル－４－メチルフェノール（０．１１ｇ、０．４９ｍｍоｌ）とテトラヒドロフラン（５４．６ｇ）を加え、５０℃で２０時間撹拌を行った。ＨＰＬＣにて反応の進行を確認後、得られた溶液にヘキサン（３００ｇ）を加え、分液ロートを用いてイオン交換水（１００ｇ）で３回洗浄を行った。その後、飽和炭酸水素ナトリウム水溶液（１００ｇ）で洗浄を行い、エバポレータで濃縮することで化合物［３］を８．３８ｇ得た。[Synthesis Example 1] Synthesis of FMAA

N-Hydroxymethylacrylamide [1] (10.0 g, 98.91 mmоl), 3,3,4,4,5,5,6,6,6-nonafluorohexane-1-ol in a 200 ml three-necked flask. [2] (13.1 g, 49.46 mmоl), phosphoric acid (0.24 g, 2.47 mmоl), 2,6-di-tertiary-butyl-4-methylphenol (0.11 g, 0.49 mmоl) Hydroxy (54.6 g) was added, and the mixture was stirred at 50 ° C. for 20 hours. After confirming the progress of the reaction by HPLC, hexane (300 g) was added to the obtained solution, and the mixture was washed 3 times with ion-exchanged water (100 g) using a separating funnel. Then, it was washed with saturated aqueous sodium hydrogen carbonate solution (100 g) and concentrated with an evaporator to obtain 8.38 g of compound [3].

<Polymerization Example 1> P1: FMAA / PEGMA 56/44
Acrylic copolymer solution (solid content concentration: 10% by mass) was obtained by dissolving 2.56 g of FMAA, 2.0 g of PEGMA, and 0.3 g of AIBN as a polymerization catalyst in 41.2 g of PMA-P and reacting at 80 ° C. for 20 hours. ) (P1) was obtained. The obtained acrylic copolymer had Mn of 22,262 and Mw of 50,083.

<Polymerization Example 2> P2: BMAA / HPMA / HEMA 40/40/20
Acrylic copolymer solution (solid content concentration) was obtained by dissolving 4.0 g of BMAA, 4.0 g of HPMA, 2.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst in 41.2 g of PM and reacting at 80 ° C. for 20 hours. 20% by mass) (P2) was obtained. The obtained acrylic copolymer had Mn of 10,103 and Mw of 25,498.

<Polymerization Example 3> P3: MOI-DEM 100
Acrylic copolymer solution (solid content concentration 20% by mass) (P3) was prepared by dissolving 10.0 g of MOI-DEM and 0.3 g of AIBN as a polymerization catalyst in 41.2 g of PM and reacting at 80 ° C. for 20 hours. Obtained. The obtained acrylic copolymer had Mn of 17,279 and Mw of 54,273.

[Preparation of cured film forming composition]
Add 0.12 g of P1 and 1.08 g of P2, 0.24 g of P3 as a cross-linking agent, and 0.12 g of PAG121 as a photoacid generator, and use PM-P 1.746 g and PMA-P 2.8020 g to make 5% by weight. It was adjusted. Further, 4.0 g of PGM-ST adjusted to 5% by weight using PM-P as fine particles was added and uniformly stirred to prepare a cured film-forming composition A1.

５００ｍＬの反応フラスコに、塩化スルフリル［キシダ化学（株）製］２７ｇ及びクロロホルム５０ｇを仕込み、撹拌して均一に溶解させた。この溶液を窒素気流下０℃まで冷却した。
別の３００ｍＬの反応フラスコに、ジチオカルバメート基を分子末端に有するハイパーブランチポリマーＨＰＳ１５ｇ及びクロロホルム１５０ｇを仕込み、窒素気流下均一になるまで撹拌した。
前述の０℃に冷却されている塩化スルフリル／クロロホルム溶液中に、窒素気流下、ＨＰＳ／クロロホルム溶液が仕込まれた前記３００ｍＬの反応フラスコから、送液ポンプを用いて、該溶液を反応液の温度が－５～５℃となるように６０分間かけて加えた。添加終了後、反応液の温度を－５～５℃に保持しながら６時間撹拌した。
さらにこの反応液へ、シクロヘキセン［東京化成工業（株）製］１６ｇをクロロホルム５０ｇに溶かした溶液を、反応液の温度が－５～５℃となるように加えた。添加終了後、この反応液をＩＰＡ１，２００ｇに添加してポリマーを沈殿させた。この沈殿をろ取して得られた白色粉末をクロロホルム１００ｇに溶解し、これをＩＰＡ５００ｇに添加してポリマーを再沈殿させた。この沈殿物を減圧ろ過し、真空乾燥して、塩素原子を分子末端に有するハイパーブランチポリマー（ＨＰＳ－Ｃｌ）８．５ｇを白色粉末として得た（収率９９％）。
得られたＨＰＳ－Ｃｌの^１Ｈ ＮＭＲスペクトルを図１に示す。ジチオカルバメート基由来のピーク（４．０ｐｐｍ、３．７ｐｐｍ）が消失していることから、得られたＨＰＳ－Ｃｌは、ＨＰＳ分子末端のジチオカルバメート基がほぼ全て塩素原子に置換されていることが明らかとなった。また、得られたＨＰＳ－ＣｌのＧＰＣによるポリスチレン換算で測定されるＭｗは１４，０００、分散度Ｍｗ／Ｍｎは２．９であった。[Synthesis Example 2] Production of HPS-Cl

Sulfuryl chloride [manufactured by Kishida Chemical Co., Ltd.] (27 g) and chloroform (50 g) were placed in a 500 mL reaction flask, and the mixture was stirred and uniformly dissolved. This solution was cooled to 0 ° C. under a nitrogen stream.
In another 300 mL reaction flask, 15 g of hyperbranched polymer HPS having a dithiocarbamate group at the molecular end and 150 g of chloroform were charged and stirred until uniform under a nitrogen stream.
From the 300 mL reaction flask in which the HPS / chloroform solution was charged in the above-mentioned sulfuryl chloride / chloroform solution cooled to 0 ° C. under a nitrogen stream, the solution was subjected to the temperature of the reaction solution using a liquid feed pump. Was added over 60 minutes so that the temperature was -5 to 5 ° C. After completion of the addition, the mixture was stirred for 6 hours while maintaining the temperature of the reaction solution at −5 to 5 ° C.
Further, a solution prepared by dissolving 16 g of cyclohexene [manufactured by Tokyo Chemical Industry Co., Ltd.] in 50 g of chloroform was added to this reaction solution so that the temperature of the reaction solution became -5 to 5 ° C. After completion of the addition, this reaction solution was added to 1,200 g of IPA to precipitate the polymer. The white powder obtained by collecting this precipitate was dissolved in 100 g of chloroform, and this was added to 500 g of IPA to reprecipitate the polymer. This precipitate was filtered under reduced pressure and dried under vacuum to obtain 8.5 g of a hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular end as a white powder (yield 99%).
The ¹ H NMR spectrum of the obtained HPS-Cl is shown in FIG. Since the peak derived from the dithiocarbamate group (4.0 ppm, 3.7 ppm) has disappeared, the obtained HPS-Cl has almost all the dithiocarbamate groups at the terminal of the HPS molecule replaced with chlorine atoms. It became clear. The Mw of the obtained HPS-Cl measured by GPC in terms of polystyrene was 14,000, and the dispersity Mw / Mn was 2.9.

凝縮器を設置した１００ｍＬの反応フラスコに、合成例２で製造したＨＰＳ－Ｃｌ ４．６ｇ（３０ｍｍｏｌ）及びクロロホルム１５ｇを仕込み、均一になるまで撹拌した。この溶液へ、ジメチルオクチルアミン［花王（株）製 ファーミン（登録商標）ＤＭ０８９８］５．０ｇ（３１．５ｍｍｏｌ）をクロロホルム７．５ｇに溶解させた溶液を加え、さらにＩＰＡ７．５ｇを加えた。この混合物を、窒素雰囲気下６５℃で４０時間撹拌した。
液温３０℃まで冷却後、溶媒を留去した。得られた残渣を、クロロホルム６０ｇに溶解し、この溶液をＩＰＥ２９０ｇに添加して再沈精製した。析出したポリマーを減圧ろ過し、５０℃で真空乾燥して、ジメチルオクチルアンモニウム基を分子末端に有するハイパーブランチポリマー（ＨＰＳ－Ｎ（Ｍｅ）_２ＯｃｔＣｌ）９．３ｇを白色粉末として得た。
得られたＨＰＳ－Ｎ（Ｍｅ）_２ＯｃｔＣｌの^１３Ｃ ＮＭＲスペクトルを図２に示す。ベンゼン環のピークと、オクチル基末端のメチル基のピークから、得られたＨＰＳ－Ｎ（Ｍｅ）_２ＯｃｔＣｌは、ＨＰＳ－Ｃｌ分子末端の塩素原子がほぼ定量的にアンモニウム基に置換されていることが明らかとなった。また、ＨＰＳ－ＣｌのＭｗ（１４，０００）及びアンモニウム基導入率（１００％）から算出されるＨＰＳ－Ｎ（Ｍｅ）_２ＯｃｔＣｌのＭｗは２８，０００となった。[Synthesis Example 3] Production of HPS-N (Me) ₂ OctCl

4.6 g (30 mmol) of HPS-Cl and 15 g of chloroform produced in Synthesis Example 2 were placed in a 100 mL reaction flask equipped with a condenser, and the mixture was stirred until uniform. To this solution was added a solution in which 5.0 g (31.5 mmol) of dimethyloctylamine [Farmin (registered trademark) DM0898 manufactured by Kao Corporation] was dissolved in 7.5 g of chloroform, and 7.5 g of IPA was further added. The mixture was stirred at 65 ° C. for 40 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., the solvent was distilled off. The obtained residue was dissolved in 60 g of chloroform, and this solution was added to 290 g of IPE for reprecipitation purification. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 9.3 g of a hyperbranched polymer (HPS-N (Me) ₂ OctCl) having a dimethyloctylammonium group at the molecular terminal as a white powder.
The ¹³ C NMR spectrum of the obtained HPS-N (Me) ₂ OctCl is shown in FIG. In the HPS-N (Me) ₂ OctCl obtained from the peak of the benzene ring and the peak of the methyl group at the terminal of the octyl group, the chlorine atom at the terminal of the HPS-Cl molecule is almost quantitatively replaced with the ammonium group. Became clear. Further, the Mw of HPS-N (Me) ₂ OctCl calculated from the Mw (14,000) of HPS-Cl and the introduction rate of ammonium groups (100%) was 28,000.

[Synthesis Example 4] Production of Pd [HPS-N (Me) ₂ OctCl] 4.6 g of palladium acetate [manufactured by Kawaken Fine Chemical Co., Ltd.] and 100 g of chloroform are uniformly charged in a 500 mL reaction flask equipped with a condenser. It was stirred until it became. A solution prepared by dissolving 5.0 g of HPS-N (Me) ₂ OctCl produced in Synthesis Example 3 in 100 g of chloroform was added to this solution using a dropping funnel. The inside of the dropping funnel was washed into the reaction flask using 100 g of chloroform and 100 g of ethanol. The mixture was stirred at 60 ° C. for 14 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., the solvent was distilled off. The obtained residue was dissolved in a mixture of 38 g of chloroform and 38 g of ethanol, and this solution was added to 750 g of IPE for reprecipitation purification. The precipitated polymer is filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 7.0 g of a complex of a hyperbranched polymer having an ammonium group at the molecular end and Pd particles (Pd [HPS-N (Me) ₂ OctCl]) in black. Obtained as a powder.
From the result of ICP emission analysis, the Pd content of the obtained Pd [HPS-N (Me) ₂ OctCl] was 31% by mass. Further, from the TEM (transmission electron microscope) image, the Pd particle size was about 2 to 4 nm.

[Reference Example 1] Preparation of electroless nickel plating solution
100 mL of Kanigen (registered trademark) blue shoemer [manufactured by Japan Kanigen Co., Ltd.] was placed in a 1 L beaker, and pure water was further added to bring the total amount of the solution to 400 mL. This solution was stirred to obtain an electroless nickel plating solution.

[Electroless plating base material B1]
The following components were mixed to prepare an electroless plating base material B1 having a hyperbranched polymer-Pd particle complex (HBP-Pd) concentration of 2% by mass.
(1) HBP-Pd: Pd [HPS-N (Me) 2OctCl] 100 parts by mass (2) Polymerizable compound (i): 8KX-078H 100 parts by mass Polymerizable compound (ii): A600 50 parts by mass (3) Photopolymerization initiator: 0.5 parts by mass with respect to the OXE01 polymerizable compound (4) Solvent: DAA-1,3BG-PhC mixed solution (mass ratio 70:25: 5) The total amount of (1) to (4) is Amount of 10,000 parts by mass

[Example 1]
[Creation of parental liquid repellent pattern]
The cured film-forming composition A1 was applied onto a silicon wafer using a spin coater, and then heat-dried on a hot plate at a temperature of 140 ° C. for 2 minutes to form a coating film having a film thickness of 200 nm. The film thickness was measured using F20 manufactured by FILMETRIS. This coating film was irradiated with ultraviolet rays having a light intensity of 100 mJ / cm ² at 365 nm for a certain period of time perpendicularly to the coating film surface by a Canon Co., Ltd. ultraviolet irradiation device PLA-600FA via a mask having a line and space pattern of 50 μm. .. Then, post-baking was performed on a hot plate at 120 ° C. for 2 minutes to prepare a pro-liquid repellent pattern.

[Contact angle measurement]
A coating film having a film thickness of 200 nm was formed on a silicon wafer of the cured film forming composition A1 with a spin coater in the same manner as described above. This coating film was divided into two regions, and one region was irradiated with ultraviolet rays having a light intensity of 100 mJ / cm ² at 365 nm for a certain period of time by the ultraviolet irradiation device PLA-600FA manufactured by Canon Inc., perpendicularly to the coating film surface. .. Next, post-baking was performed on a hot plate at 120 ° C. for 2 minutes, and the contact angle of the electroless plating substrate B1 was measured for the unexposed portion and the exposed portion of the obtained coating film (hereinafter, this region is referred to as this region). The "exposed area" and the other areas are referred to as "unexposed areas"). The contact angle was measured using a fully automatic contact angle meter CA-W (manufactured by Kyowa Interface Science Co., Ltd.) in a constant temperature and humidity environment (25 ° C ± 2 ° C, 50% RH ± 5%). The results are shown in Table 1.

Using an inkjet system, the electroless plating substrate B1 was appropriately adjusted to drive waveform: B, repetition frequency: 1 kHz, and drive voltage around 10 V on the prepared liquid-repellent pattern, and one drop was discharged every 30 μm.
The substrate on which the fine lines were drawn was heated at 120 ° C. for 5 minutes, photo-cured by irradiating with ultraviolet light having an exposure amount of 600 mJ / cm ² , and then heated at 120 ° C. for 2 minutes.
For the obtained pattern, a digital microscope image was observed and the shape of the fine line pattern was evaluated. The evaluation criteria were visually evaluated according to the following.
It was immersed in the plating solution prepared in Reference Example 1 at 90 ° C. for 2 minutes. After that, the removed substrate was washed with water and air-dried. Regarding the plated fine wire pattern, the digital microscope image was observed, and it was confirmed that the fine wire plating was deposited according to the pattern.

<Shape evaluation criteria>
A: High straightness and almost constant line width B: Some areas where the line width is wide are observed C: Straightness is low and the line width is not stable

[Comparative Example 1]
The contact angle of the electroless plating base material B1 was measured on the silicon wafer by the same operation as in Example 1.
Next, using an inkjet system in the same operation as in Example 1, the electroless plating base material B1 was discharged onto a silicon wafer, and the shape of the cured fine wire pattern was evaluated.

[Evaluation results]
The results of the above evaluation are shown in Table 1.

As shown in Table 1, a fine line is drawn by inkjet using an electroless plating base agent on a pattern applied on a film having a parent liquid portion and a liquid repellent portion to form a base layer, and a plating film is formed on the base layer. When it was formed (Example 1), it was possible to form a pattern having high straightness and no disconnection following the electroless liquid pattern.
On the other hand, when the catalyst ink was drawn on a silicon wafer having no liquid-repellent pattern (Comparative Example 1), the liquid was greatly wetted and spread, and a straight-line pattern could not be obtained.
From the above results, it was clarified that a metal fine line pattern having high straightness can be obtained by inkjet drawing an electroless plating substrate on the liquid-repellent pattern.

Claims (7)

The following steps A and B :
Step A: A step of providing a base layer by applying a catalyst ink on a base material having a parent liquid portion and a liquid repellent portion.
Step B: A step of immersing a base material provided with a base layer in an electroless plating bath to form a metal plating film.
Including
The base material having the parent liquid portion and the liquid repellent portion is a base material formed by forming a film having the parent liquid portion and the liquid repellent portion on the base material.
The film having the parental liquid portion and the liquid-repellent portion has a liquid-repellent portion having a liquid-repellent group and a parent-liquid portion that is made liquid-repellent by the desorption or decomposition of the liquid-repellent group by exposure. A film or a film having a liquid-repellent portion having a liquid-repellent group and a parent-liquid portion made liquid-friendly by the desorption of the liquid-repellent group by the action of an acid generated by exposure.
The membrane having the parent liquid part and the liquid repellent part,
It is formed by a polymer containing a structural unit derived from a monomer having the structure of the following formula (1) as a component (A), a photoacid generator as a component (B), and a photoparent liquid repellent portion forming composition containing a solvent. This is a wiring formation method.

(In the formula, R ¹¹ represents a hydrogen or methyl group and R ¹² represents an organic group that can be desorbed with an oxygen atom to which it is attached.) The catalyst ink is (a) dispersant,
(B) Metal fine particles,
(C) The wiring forming method according to claim 1, which is a wiring forming method ink containing a solvent. A hyperbranched polymer in which the catalytic ink has (a) an ammonium group at the molecular end and a weight average molecular weight of 1,000-5,000,000.
(B) Metal fine particles,
(C) The wiring forming method according to claim 1, which is a wiring forming method ink containing a solvent. The wiring forming method according to claim 1, wherein the film having the parent liquid portion and the liquid repellent portion is formed by a photoparent liquid repellent portion forming composition further containing fine particles as the component (C). 2. The wiring forming method described in any one of them. A base material for which wiring is formed by using the wiring forming method according to any one of claims 1 to 5. An apparatus comprising the substrate according to claim 6.