TWI486411B - Surface treatment agent - Google Patents

Description

Surface treatment agent

The present invention relates to a surface treatment agent capable of forming a fine pattern film or a solid film having less unevenness when a predetermined solid film or pattern film is formed on a substrate by a printing method such as an inkjet method.

The patterned transparent film is used in many parts of a liquid crystal display element such as a spacer, an insulating film, or a protective film. To date, various photosensitive compositions have been used for such applications.

Further, in recent years, printing methods typified by an inkjet method have been used, and an inkjet method capable of forming an on-demand pattern is excellent in the environment and can also be expected to cost merit. Having attention.

In addition, in recent years, it is also required to realize a fine pattern which is superior to a pattern obtained by a photolithographic method by an inkjet method, but in the current inkjet method, the ink is wet-diffused after the ink is sprayed. And the amount of liquid discharged at one time is large, so it is difficult to achieve this requirement.

In order to draw a fine pattern on a substrate by an inkjet method, it is necessary to perform surface treatment (ink repellency treatment) of the substrate. As a method of surface treatment, for example, Japanese Patent Laid-Open Publication No. 2005-251809 and Japanese Patent Laid-Open No. 2004- The technique described in the publication No. 6700. In the techniques described in these documents, plasma treatment using a fluorocarbon gas such as tetrafluoromethane or by heptafluoro-1,1,2,2-tetrahydroanthracene is used. The fluoroalkyl decane such as triethoxy decane is placed in the same container and placed in the same container for a certain period of time to perform surface treatment of the substrate.

However, in the plasma processing method, an appropriate device is required, and there are problems in terms of a process such as a cost and a phenomenon in which a toxic gas is generated; and in the method of placing a certain time, the following problems exist. : The time required for surface treatment is long, and the manufacturing efficiency of the final product is poor. Therefore, a method of easily performing surface treatment on a substrate is required.

Further, a polymer composition capable of forming a water-sliding surface is disclosed in Japanese Laid-Open Patent Publication No. 2000-239601, which is characterized in that a hydroxane polymer (A) containing a hydrolyzable alkoxyalkyl group is required as a necessity. The component, the hydrolyzable alkoxyalkylalkyl group-containing alkoxyalkyl polymer (A) is obtained by copolymerization of the following components: (a) a macromonomer represented by the following formula (macromonomer) And/or a specific alkoxyalkyl macromonomer 1 wt% to 40 wt%, (b) a hydrolyzable alkoxyalkyl group-containing monomer 5 wt% to 50 wt%, and (c) may be The other unsaturated monomers in which the compound is copolymerized are from 10 wt% to 94 wt%.

[Chemical 1]

In the above formula, Z ¹ represents an alkyl group having 1 to 10 carbon atoms, Z ² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z ³ represents a hydrogen atom or a methyl group, and y is a number of 6 to 300.

In Japanese Patent Laid-Open Publication No. 2000-239601, it is disclosed that the polymer composition is used for the purpose of forcing water on an object, even if the water is not forced by mechanical means such as wiping off. If it is removed sexually, it is also possible to tilt the object and roll the attached water droplets.

An object of the present invention is to provide a surface treatment agent capable of easily performing an ink repellent treatment on a substrate even when a fine pattern film can be formed in a printing method such as an inkjet method.

Further, when the substrate is subjected to a surface treatment, a surface treatment film is formed on the substrate. However, since the material constituting the electronic component is too high, the ink repellency (liquid repellency) of the surface treatment film is too high, and the substrate of the material is The surface treatment film) has insufficient wettability. In consideration of such a case, it is preferred that the surface treatment film can be easily removed when a material having low wettability is applied onto a substrate. Another object of the present invention is to provide a surface treatment agent which can form a surface treatment film which can be easily removed.

Further, when a solid film is formed on a substrate by an inkjet method, a solid film is usually formed by ejecting ink on an inkjet head while reciprocating a plurality of times on the substrate. In this case, there is a phenomenon in which the ink sprayed on the substrate spreads and the ink is partially applied repeatedly. The thickness of the ink film constituting the portion to be repeatedly applied was thicker than the portion where the repeated coating was not formed, and as a result, irregularities were formed on the solid film, and a flat solid film could not be obtained.

Accordingly, an object of the present invention is to provide a surface treatment agent capable of preventing the above-described ink from being wet-diffused by imparting ink repellency to a substrate, thereby forming a flat solid film having no unevenness.

Further, in the present specification, the solid film is a film in which the entire surface of the substrate surface is covered with a material (ink) constituting the electronic component, and the pattern film refers to a portion where the surface of the substrate is exposed and is composed of electronic components. A film formed of the material in the case of a portion covered by the material (ink).

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a copolymer containing a structural unit derived from a specific compound containing ruthenium and a radically polymerizable monomer having a hydrophilic group is found. The surface treatment agent derived from the structural unit) and the solvent can impart excellent ink repellency to the substrate, and can form a surface treatment film which can be easily removed, thereby completing the invention.

The present invention includes the following matters.

[1] A surface treatment agent for imparting ink repellency to a substrate, characterized in that it comprises a copolymer and a solvent (e), wherein the copolymer has a compound (a) represented by the following formula (1) The structural unit derived from the structural unit derived from the radical polymerizable monomer (b) having a hydrophilic group:

[Chemical 2]

(In the formula (1), R ¹ , R ² and R ⁵ each independently represent hydrogen or a linear or branched alkyl group having 1 to 30 carbon atoms, and any methyl group in the alkyl group may be used. Substituted by a cycloalkyl group, any discontinuous methylene group may be substituted by -O- or a cycloalkyl group, and any methine group may be substituted by cycloalkane triyl, any methane tetra group. (methanetetrayl) may also be substituted by a cycloalkyltetrayl group, and R ³ and R ⁴ each independently represent hydrogen, a linear or branched alkyl group having 1 to 30 carbon atoms or a group represented by the following formula (2) In the alkyl group, any methyl group may be substituted by a cycloalkyl group, and any discontinuous methylene group may be substituted by -O- or a cycloalkyl group, and any methine group may also be substituted by a ring. Alkyntriyl substitution, any methane tetrayl group may be substituted by a cycloalkyltetrayl group, n is an integer of from 1 to 1,000, and when n is 2 or more, a plurality of R ³ and R ⁴ may be the same or different Different, A ¹ represents a radical polymerizable functional group);

[Chemical 3]

(In the formula (2), R ⁶ , R ⁷ and R ⁸ each independently represent hydrogen or a linear or branched alkyl group having 1 to 30 carbon atoms, and any methyl group may be used in the alkyl group. Substituted by a cycloalkyl group, any discontinuous methylene group may be substituted by -O- or a cycloalkyl group, and any methine group may be substituted by a cycloalkane group, and any methane tetra group may also be substituted by a ring. The alkynyl group is substituted, and m is an integer of from 1 to 500. When m is 2 or more, a plurality of R ⁶ and R ⁷ may be the same or different.

[2] The surface treatment agent according to [1], wherein the hydrophilic group in the radical polymerizable monomer (b) is a hydroxyl group, a carboxyl group or a phenolic hydroxyl group.

[3] The surface treatment agent according to [1], wherein the copolymer further has a structural unit derived from a radical polymerizable monomer (c) other than the radical polymerizable monomer (b) .

[4] The surface treatment agent according to [1], wherein in the general formula (1) and the general formula (2), the linear or branched alkyl group has a carbon number of from 1 to 20, A. ¹ is a (meth) propylene methoxyalkyl group, a (meth) propylene group or a vinyl group, and m is an integer of from 1 to 300.

[5] The surface treatment agent according to any one of [1] to [4] wherein the compound (a) is 3-methacryloxypropyl tris (trimethylnonane) Oxy) decane or a compound represented by the following formula (3):

[Chemical 4]

(In the formula (3), R ⁹ is hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, and any methyl group may be substituted by a cycloalkyl group in the alkyl group, and any The continuous methylene group may also be substituted by -O- or a cycloalkyl group, and any methine group may be substituted by a cycloalkane group, and any methane tetra group may also be substituted by a cycloalkane group, n is 1 to An integer of 1000).

[6] The surface treatment agent according to [1], wherein the radical polymerizable monomer (b) is (meth)acrylic acid or 4-hydroxyphenylvinylketone.

[7] The surface treatment agent according to [3], wherein the radical polymerizable monomer (c) is N-phenylmaleimide, dimethylaminoethyl (meth)acrylate or Butyl (meth)acrylate.

[8] A method of imparting ink repellency to a substrate, comprising the step of forming a surface treatment film on a substrate using the surface treatment agent according to [1].

[9] A method of forming a pattern film by forming a pattern film having a width of 200 μm or less on a substrate to which ink repellent property is imparted by the method according to [8] by an inkjet coating method method.

[10] An electronic component comprising: a pattern film formed by the method according to [9].

[11] A method of producing an electronic component, comprising: forming a surface treatment film on a substrate using the surface treatment agent according to [1], and forming a solid film or a pattern film on the surface treatment film.

[Effect of the invention]

Since the surface treatment film formed by the surface treatment agent of the present invention exhibits ink repellent properties to the ink droplets ejected by the ink jet, a fine pattern film and a flat solid film can be formed by ink ejection. Further, the surface treatment film which becomes useless can be easily removed by an alkaline aqueous solution or the like. Therefore, the surface treatment agent of the present invention is most suitable for use in forming an electronic circuit pattern on a substrate or the like.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

The surface treatment agent (hereinafter also referred to simply as "the surface treatment agent of the present invention") for imparting ink repellency to the substrate of the present invention comprises a copolymer having a compound represented by the following formula (1) (a) a structural unit derived, a structural unit derived from a radical polymerizable monomer (b) having a hydrophilic group, and a solvent (e).

[Compound (a) represented by the formula (1)]

The structural unit derived from the compound (a) represented by the following formula (1) (hereinafter also referred to simply as "structural unit (a)"), which is a copolymer contained in the surface treatment agent of the present invention, is imparted A sufficient ink repellency function required for the substrate to form a fine patterned film.

[Chemical 5]

In the formula (1), R ¹ , R ² and R ⁵ each independently represent hydrogen or a linear or branched alkyl group having 1 to 30 carbon atoms, and in the alkyl group, any methyl group may be Substituted by a cycloalkyl group, any discontinuous methylene group may be substituted by -O- or a cycloalkyl group, and any methine group may be substituted by a cycloalkane group, and any methane tetra group may also be substituted by a naphthenic group. a tetra-substituent, wherein R ³ and R ⁴ each independently represent hydrogen, a linear or branched alkyl group having 1 to 30 carbon atoms, or a group represented by the following formula (2), in the alkyl group, Any methyl group may be substituted by a cycloalkyl group, and any discontinuous methylene group may be substituted by -O- or a cycloalkyl group, and any methine group may be substituted by a cycloalkane group, and any methane may be substituted. The tetra group may be substituted by a cycloalkane group, and n is an integer of from 1 to 1,000. When n is 2 or more, a plurality of R ³ and R ⁴ may be the same or different, and A ¹ represents a radical polymerization. Sex functional group.

[Chemical 6]

In the formula (2), R ⁶ , R ⁷ and R ⁸ each independently represent hydrogen or a linear or branched alkyl group having 1 to 30 carbon atoms, and in the alkyl group, any methyl group may be Substituted by a cycloalkyl group, any discontinuous methylene group may be substituted by -O- or a cycloalkyl group, and any methine group may be substituted by a cycloalkane group, and any methane tetra group may also be substituted by a naphthenic group. The tetra group is substituted, and m is an integer of from 1 to 500. When m is 2 or more, a plurality of R ⁶ and R ⁷ may be the same or different.

In the "linear or branched alkyl group having 1 to 30 carbon atoms" described in the description of the above formulas (1) and (2), the methine group is a structure in which three hydrogens are removed from methane. It is present in the case where one branch is formed in any of the carbons constituting the alkyl group, and the so-called methane tetra group is a structure in which four hydrogens are removed from methane, and two points are formed in carbon constituting one of the alkyl groups. The situation of the branch exists.

For example, examples of the structure in which the alkyl group is a pentyl group and one methylene group constituting the pentyl group is substituted by a cyclohexyl group can be exemplified below. In addition, in the following structure, "*" represents a chemical bond.

[Chemistry 7]

Further, examples of the structure in which the alkyl group is a 5-propyloctyl group and the methine group constituting the 5-propyloctyl group is substituted with a cyclohexane triyl group are as follows. In addition, in the following structure, "*" represents a chemical bond.

[化8]

The number of carbon atoms of the above cycloalkyl group, cycloalkylene group, cycloalkanetriyl group and cycloalkane group is usually 4 to 12, and preferably 5 to 10, more preferably from the viewpoint of imparting excellent ink repellency to the substrate. It is 6-8.

The carbon number of the linear or branched alkyl group having 1 to 30 carbon atoms is preferably from 1 to 25, more preferably from 1 to 20, from the viewpoint of imparting excellent ink repellency to the substrate. Further, in the linear or branched alkyl group, when it is judged whether or not the alkyl group corresponds to the "linear or branched alkyl group having 1 to 30 carbon atoms", it may be substituted for The number of carbon atoms such as a cycloalkyl group such as an alkyl group is set to 1. That is, for example, 12-(5-fluorenyl)cyclodecyldodecyl group represented by the following formula corresponds to a linear or branched alkyl group having 1 to 30 carbon atoms in the present invention.

[Chemistry 9]

In the above formula, "*" represents a chemical bond.

From the viewpoint of imparting excellent ink repellency to the substrate, R ¹ , R ² and R ^{5 are} preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

From the viewpoint of imparting excellent ink repellency to the substrate, R ³ and R ^{4 are} preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

Further, in the formula (1), n is an integer of from 1 to 1,000, and is preferably an integer of from 1 to 500, more preferably an integer of from 1 to 300, from the viewpoint of imparting excellent ink repellency to the substrate.

Further, in the formula (1), A ¹ represents a radical polymerizable functional group. The term "radical polymerizability" refers to a property in which polymerization is started by radicals generated by irradiation of light or heating. Examples of the radical polymerizable functional group include a (meth)acryloxyalkyl group, a (meth)acryl group, and a vinyl group. Of these groups, particularly preferred are (meth)acryloxyalkyl groups. Further, the alkyl group in the (meth)acryloxyalkyl group usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

In the above formula (2), R ⁶ , R ⁷ and R ^{8 are} preferably an alkyl group having 1 to 8 carbon atoms, more preferably a carbon number, from the viewpoint of imparting excellent ink repellency to the substrate. Alkyl groups of 1 to 4.

Further, in the formula (2), m is an integer of from 1 to 500, but from the viewpoint of imparting excellent ink repellency to the substrate, an integer of from 1 to 300 is preferable, and an integer of from 1 to 100 is more preferable. .

Preferable specific examples of the compound (a) include 3-methacryloxypropyltris(trimethyldecyloxy)decane and monomethylpropene oxime represented by the following formula (3). Base end - dimethyl methoxy alkane.

[化10]

In the formula (3), R ⁹ is hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, and in the alkyl group, any methyl group may be substituted by a cycloalkyl group, and any discontinuity thereof The methylene group may also be substituted by -O- or a cycloalkyl group, and any methine group may be substituted by a cycloalkane group, and any methane tetra group may be substituted by a cycloalkane group, n is from 1 to 1000. The integer.

In the formula (3), R ^{9 is} preferably a butyl group, and n is preferably an integer of from 1 to 100 from the viewpoint of imparting excellent ink repellency to the substrate.

In the case of producing the copolymer contained in the surface treatment agent of the present invention, the above compound (a) may be used alone or in combination of two or more.

Further, a method for producing the compound (a) is well known and commercially available.

[Free radical polymerizable monomer (b) having a hydrophilic group]

The structural unit derived from the radical polymerizable monomer (b) having a hydrophilic group (hereinafter also referred to simply as "structural unit (b)") imparts alkali solubility to the copolymer contained in the surface treatment agent of the present invention. Further, the surface treatment film formed by coating the surface treatment agent of the present invention on the substrate, drying the coating film, or calcining the coating film can be easily removed by an aqueous alkaline solution.

The radical polymerizable monomer (b) is not particularly limited as long as it is a compound having a hydrophilic group and capable of undergoing radical polymerization.

The hydrophilic group may, for example, be a hydroxyl group, a carboxyl group, a phenolic hydroxyl group or an amine group. From the viewpoint of easiness of removing the surface treatment film and imparting ink repellency, the hydrophilic group is preferably a hydroxyl group or a carboxyl group. Phenolic hydroxyl group.

Specific examples of the radically polymerizable monomer (b) having such a hydrophilic group include a radical polymerizable monomer having an unsaturated carboxylic acid moiety such as (meth)acrylic acid, itaconic acid or vinyl acetic acid, and 4 a radical polymerizable monomer having a phenolic hydroxyl group such as hydroxyphenyl vinyl ketone or hydroxystyrene.

Preferred from the viewpoint of improving the alkali solubility of the surface-treating film of the present invention, (meth)acrylic acid and 4-hydroxyphenylvinylketone are preferred among the compounds.

In the case of producing the copolymer contained in the surface treatment agent of the present invention, the above-mentioned radical polymerizable monomer (b) may be used alone or in combination of two or more.

[The radically polymerizable monomer (c) other than the radically polymerizable monomer (b)] The copolymer contained in the surface treatment agent of the present invention, in addition to the above structural unit (a) and structural unit (b), It is also possible to have a structural unit derived from a radical polymerizable monomer (c) other than the radical polymerizable monomer (b) (hereinafter also referred to simply as "structural unit (c)"). The copolymer improves the coatability of the surface treatment agent of the present invention to the substrate by having the structural unit (c).

The radical polymerizable monomer (c) is not particularly limited as long as it is a radical polymerizable monomer other than the radical polymerizable monomer (b), and is, for example, a (meth) acrylate having an unsaturated carboxylic anhydride moiety. A radical polymerizable monomer, a vinyl compound, and a quinone imine compound. Examples of the radical polymerizable monomer having an unsaturated carboxylic anhydride moiety include maleic anhydride and itaconic anhydride.

Specific examples of the radical polymerizable monomer (c) include N-phenylmaleimide, cyclohexylmaleimide, maleic anhydride, itaconic anhydride, vinyl acetate, and dimethylamine acrylate. Ethyl ethyl ester, dicyclopentyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate. Preferred among these compounds are N-phenylmaleimide, dimethylaminoethyl (meth)acrylate and butyl (meth)acrylate from the viewpoint of improving coatability.

In the case of producing the copolymer contained in the surface treatment agent of the present invention, the above-mentioned radical polymerizable monomer (c) may be used alone or in combination of two or more.

<Copolymerization method of copolymer>

The polymerization method of the compound (a), the radically polymerizable monomer (b), and the radically polymerizable monomer (c) used as needed is not particularly limited, and a usual radical polymerization method can be employed.

For example, the mixture of the compound (a), the radical polymerizable monomer (b), and the radical polymerizable monomer (c) can be stirred and refluxed in a solvent to carry out radical polymerization to obtain the present invention. The copolymer contained in the surface treatment agent. Further, the solvent used as a polymerization solvent can also be directly used as the solvent (e) to be described later.

It is preferred to carry out radical polymerization by adding a polymerization initiator (d). The polymerization initiator (d) is usually a compound which generates a radical by heat, and specific examples thereof include azobisisobutyronitrile and 2,2-azobis(2-methylpropionic acid) dimethyl ester. An azo-based initiator and a peroxide-based initiator such as benzamidine peroxide.

The reflux temperature in the polymerization reaction is the boiling point of the solvent to be used, and must be a temperature at which radicals are sufficiently generated from the polymerization initiator (d). The boiling point of the solvent satisfying such conditions is usually in the range of 50 ° C to 150 ° C.

The reflux time is also not particularly limited and is usually in the range of 1 hour to 24 hours. Further, the polymerization can also be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

Further, in order to adjust the molecular weight of the copolymer, a chain transfer agent such as thioglycolic acid may be added in an appropriate amount in the polymerization reaction system.

<Composition ratio of copolymer>

In the copolymer contained in the surface treatment agent of the present invention produced in the above manner, the composition ratio of the structural unit (a) is relative to the structural unit from the viewpoint of exhibiting the ink repellent property of the surface treatment film. And 100 wt% of the structural unit (b) is preferably from 1 wt% to 95 wt%, more preferably from 5 wt% to 90 wt%, still more preferably from 10 wt% to 85 wt%. .

Further, the composition ratio of the structural unit (b) in the copolymer is from the viewpoint of improving the solubility of the surface treatment film in the alkaline aqueous solution, with respect to the total of the structural unit (a) and the structural unit (b) The wt% is preferably from 5 wt% to 99 wt%, more preferably from 10 wt% to 95 wt%, still more preferably from 15 wt% to 90 wt%.

The copolymer may also have a structural unit (c). In this case, the composition ratio of the structural unit (c) is preferably 10% by weight to 90% by weight based on 100% by weight of the copolymer, more preferably It is 20 wt% to 87 wt%, and more preferably 25 wt% to 85 wt%.

The composition ratio of the structural unit derived from each compound can be adjusted by adjusting the loading amount of the compound (a), the radical polymerizable monomer (b), and the radical polymerizable monomer (c) in the polymerization reaction. For the above range.

<weight average molecular weight of copolymer>

The weight average molecular weight of the copolymer contained in the surface treatment agent of the present invention is not particularly limited, but is usually from 1,000 to 100,000, and from the viewpoint of coatability, it is preferably from 5,000 to 50,000. In the present specification, the weight average molecular weight is a weight average molecular weight in terms of standard polystyrene measured by GPC. More specifically, the LC-10AT system manufactured by Shimadzu Corporation, RID-6A (RI detector), CTO-6A (column oven) was used as the GPC apparatus, and the THF piping column manufactured by POLYMER Laboratories was used. PLgel 5 μm MIXED-D column) The polystyrene conversion value obtained by the GPC method (column temperature: 35 ° C, flow rate: 1 ml/min) as a column.

The weight average molecular weight of the copolymer can be adjusted by adjusting the kind of the compound (a) (the number of n and m in the formula (1) and the formula (2)), the reflux time, the addition amount of the polymerization initiator, and the like. For the above range.

[solvent (e)]

In the surface treatment agent of the present invention, the solvent (e) is contained in order to improve the coatability of the treatment agent. The solvent (e) is preferably a solvent which can dissolve the compound (a) and the radical polymerizable monomer (b) and further dissolve the radical polymerizable monomer (c). The reason for this is that when such a solvent is used for the production of the copolymer, if the solvent remains at the end of the polymerization reaction, it can be directly used as the solvent (e).

The solvent (e) used in the present invention preferably has a boiling point of 50 ° C to 250 ° C from the viewpoint of easiness of drying the surface treatment agent of the present invention applied to the substrate.

Specific examples of the solvent (e) having a boiling point of 50 ° C to 250 ° C include methanol, methyl ethyl ketone, ethanol, 1-propanol, 2-propanol, ethyl acetate, xylene, toluene, hexane, isobutanol, Methyl isobutyl ketone, methyl butyl ketone, acetone, methyl 3-methoxypropionate, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl Ethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol butyl methyl ether, dipropylene glycol methyl ether acetate, triethylene glycol Alcohol dimethyl ether, tripropylene glycol monomethyl ether and tripropylene glycol dimethyl ether.

When the surface treatment agent is applied to a substrate and then used as a surface treatment film without being calcined, it is preferred to use a low boiling point solvent such as ethanol, acetone or methyl ethyl ketone.

The solvent (e) used in the present invention may be a single compound or a mixed solvent of two or more kinds.

Further, in the surface treatment agent of the present invention, it is preferred to prepare the solvent (e) such that the copolymer of the solid matter is 0.01 wt% to 50 wt% with respect to the total amount of the copolymer and the solvent (e).

Further, the preferred solid content concentration varies depending on the coating method of the surface treatment agent of the present invention. For example, when the surface treatment agent is applied by the dipping method, the solid content concentration is preferably 0.01 wt% to 30 wt%, more preferably 0.05 wt% to 20 wt%; and coated with a cloth or the like. In the case of the method, the solid concentration is preferably 0.01 wt% to 20 wt%, more preferably 0.5 wt% to 15 wt%; in the case of the spin coating method, the solid concentration is preferably 0.01 wt%. ～50 wt%, more preferably 0.05 to 40 wt%.

[additive]

In the surface treatment agent for imparting ink repellency to the substrate of the present invention, an additive may be added as needed in order to improve coating uniformity, adhesion between the surface treatment film and the substrate, alkali solubility, and the like. Examples of the additives include anionic, cationic, nonionic, fluorine- or quinone-based surfactants, adhesion promoters such as decane coupling agents, and ultraviolet absorbers such as alkoxybenzophenones.

[Preservation of surface treatment agent]

When the surface treatment agent for imparting ink repellency to the substrate of the present invention is stored in a light-shielding manner at a temperature of from -30 ° C to 30 ° C, the stability over time is good. If the storage temperature is -10 ° C to 20 ° C, there is no precipitate and it is more preferable.

[Coating method of surface treatment agent of the present invention]

The surface treatment film of the surface treatment agent of the present invention can be formed by applying a surface treatment agent to a substrate such as glass by a method generally performed in the field of inkjet or other known methods.

Examples of the coating method include spin coating, roll coating, slit coating, or an inkjet method, a screen printing method, and the like.

Examples of the substrate to which the surface treatment agent of the present invention is applied include a transparent glass substrate such as white plate glass, blue plate glass, ceria coated green plate glass, polycarbonate, polyether oxime, polyester, acrylic resin, and polychlorinated chloride. a synthetic resin sheet, a film or a substrate made of a vinyl resin, an aromatic polyamide resin, a polyamide, a phthalimide or a polyimide, a metal plate such as an aluminum plate, a copper plate, a nickel plate or a stainless steel plate, or another ceramic plate. A semiconductor substrate or the like having a photoelectric conversion element.

These substrates do not have to be planar, and may be curved when they are coated with the surface treatment agent of the present invention.

Further, the surface treatment agent of the present invention may be impregnated into the pulverized yarn, the cloth or the like without using the above method, and the surface treatment agent of the present invention may be applied to the substrate by wiping the surface of the substrate, or The substrate is immersed in the surface treatment agent together, and after a predetermined period of time, it is taken out and applied.

The substrate coated with the surface treatment agent by the above method may be directly air-dried or calcined to further improve the adhesion or reliability of the surface treatment film to the substrate. The calcination temperature is not particularly limited as long as the solvent (e) in the surface treatment agent is dried, and is preferably 50 to 300 ° C, more preferably 70 to 250 ° C, still more preferably 80. °C ~ 230 °C.

When the surface repellency of the surface-treated substrate is imparted, a desired pattern can be formed on the substrate (specifically, on the surface-treated film) by an inkjet method, a screen printing method, or the like, and the width can be normally formed. 200 μm or less, preferably a fine pattern film having a width of 100 μm or less. Further, when a solid film is formed by an inkjet method, ink is imparted to the substrate to obtain ink repellency, and the ink is not wet-diffused, and even if the ink-jet method is applied, the portion to be repeatedly coated does not appear, and the unevenness is not flat. Solid film.

Further, after the pattern or the like is drawn, the surface-treated portion of the portion which becomes unnecessary may be easily removed by an alkaline aqueous solution or the like.

<Do not remove part of the surface treatment film>

When a desired pattern or the like is drawn with ink by an inkjet method, a screen printing method, or the like, and a material having insufficient wettability to the surface treatment film is further applied, the portion formed in the coating material is not formed. The surface treatment film can be easily removed by an aqueous alkaline solution.

Specific examples of the base contained in the alkaline aqueous solution include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, sodium hydrogencarbonate, and carbonic acid. Potassium, potassium bicarbonate, sodium hydroxide and potassium hydroxide.

In the alkaline aqueous solution, methanol, ethanol or a surfactant may be added in order to increase the solubility of the surface treatment film to the alkaline aqueous solution. As the surfactant, for example, an anionic, cationic or nonionic surfactant can be used.

The concentration of the alkaline aqueous solution is not particularly limited, and is preferably 0.01 wt% to 10 wt%, more preferably 0.05 wt% to 5 wt%, still more preferably 0.1 wt% to 3 wt%. Further, the time during which the substrate is immersed in the alkaline aqueous solution is not particularly limited as long as the surface treatment film can be completely removed, and preferably 30 seconds to 120 seconds, more preferably 40 seconds to 100 seconds. Further better is 50 seconds to 90 seconds. Further, the temperature of the alkaline aqueous solution is not particularly limited, and is usually 15 ° C to 35 ° C, preferably 20 ° C to 30 ° C.

After forming a fine pattern film on the substrate as described above, an electronic component called a liquid crystal display element is produced by a predetermined manufacturing process such as applying color ink. A fine patterned film can be formed on the surface-treated substrate by the surface treating agent of the present invention, so that a smaller electronic component can be obtained.

[Example]

Hereinafter, the present invention will be further illustrated by way of examples, but the invention is not limited to the examples.

In the following, the compound (a), the radical polymerizable monomer (b), the radical polymerizable monomer (c), and the polymerization used in the synthesis example and the comparative synthesis example are indicated by the following symbols. Starting agent (d) and solvent (e).

<compound (a)>

A-1: 3-methacryloxypropyltris(trimethyldecyloxy)decane

A-2: α-butyl-ω-(3-methylpropenyloxypropyl)polydimethyloxane (in the above formula (3), R ⁹ is n-butyl group, and n is 2 Compound).

<Free radical polymerizable monomer (b)>

B-1: methacrylic acid

B-2: 4-hydroxyphenyl vinyl ketone.

<Free radical polymerizable monomer (c)>

C-1: butyl methacrylate

C-2: N-phenyl maleimide

C-3: dimethylaminoethyl acrylate.

<Polymerization initiator (d)>

D-1: 2,2-azobis(2-methylpropionic acid) dimethyl ester.

<solvent (e)>

E-1: methyl ethyl ketone.

[Synthesis Example 1] Synthesis of Copolymer (A1)

Into a four-necked flask equipped with a stirrer, α-butyl-ω-(3-methylpropenyloxypropyl)polydimethyloxane as a compound (a) was charged in the following weight ratio. (a-2), methacrylic acid (b-1) as the radical polymerizable monomer (b), butyl methacrylate (c-1) as the radical polymerizable monomer (c), and polymerization 2,2-azobis(2-methylpropionic acid) dimethyl ester (d-1) as initiator (d), butanone (e-1) as solvent (e), carried out at 80 ° C 2 hours of reflux.

A-2 8.100 g

B-1 2.025 g

C-1 3.375 g

D-1 2.025 g

E-1 27.0 g.

The reaction mixture was cooled to room temperature to obtain a copolymer (A1). A portion of the solution was sampled and the weight average molecular weight of the copolymer (A1) was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 15,000.

[Synthesis Example 2] Synthesis of Copolymer (A2)

In the same manner as in Synthesis Example 1, the following components were charged in the following weight ratios, and refluxed.

A-1 8.100 g

B-1 2.025 g

C-1 3.375 g

D-1 2.025 g

E-1 27.0 g.

The same treatment as in Synthesis Example 1 was carried out, and the weight average molecular weight determined by GPC analysis (polystyrene standard) of the obtained copolymer (A2) was 14,800.

[Synthesis Example 3] Synthesis of Copolymer (A3)

In the same manner as in Synthesis Example 1, the following components were charged in the following weight ratios, and refluxed.

A-1 11.475 g

B-1 2.025 g

The same treatment as in Synthesis Example 1 was carried out, and the weight average molecular weight determined by GPC analysis (polystyrene standard) of the obtained copolymer (A3) was 15,800.

[Synthesis Example 4] Synthesis of Copolymer (A4)

In the same manner as in Synthesis Example 1, the following components were charged in the following weight ratios, and refluxed.

The same treatment as in Synthesis Example 1 was carried out, and the weight average molecular weight of the obtained copolymer (A4) as determined by GPC analysis (polystyrene standard) was 15,200.

[Synthesis Example 5] Synthesis of Copolymer (A5)

In the same manner as in Synthesis Example 1, the following components were charged in the following weight ratios, and refluxed.

The same treatment as in Synthesis Example 1 was carried out, and the weight average molecular weight of the obtained copolymer (A5) as determined by GPC analysis (polystyrene standard) was 16,200.

[Comparative Synthesis Example 1] Comparison of Synthesis of Copolymer (B1)

In the same manner as in Synthesis Example 1, the following components were charged in the following weight ratios, and refluxed.

B-1 2.025 g

C-3 11.475 g

D-1 2.025 g

E-1 27.0 g.

The same treatment as in Synthesis Example 1 was carried out, and the weight average molecular weight determined by GPC analysis (polystyrene standard) of the comparative copolymer (B1) was 13,900.

[Comparative Synthesis Example 2] Comparison of Synthesis of Copolymer (B2)

In the same manner as in Synthesis Example 1, the following components were charged in the following weight ratios, and refluxed.

B-2 2.7 g

C-3 10.8 g

D-1 2.025 g

E-1 27.0 g.

The same treatment as in Synthesis Example 1 was carried out, and the weight average molecular weight determined by GPC analysis (polystyrene standard) of the comparative copolymer (B2) was 16,100.

[Examples 1 to 5, Comparative Examples 1 to 4]

<Formation of surface treatment film>

The copolymer obtained in Synthesis Example 1 to Synthesis Example 5 and Comparative Synthesis Example 1 and Comparative Synthesis Example 2 was diluted to 333 times with methyl ethyl ketone to prepare a surface treatment agent.

The obtained surface treatment agent was spin-coated on a glass substrate at 3000 rpm for 10 seconds, and air-dried directly to form a surface-treated film on the glass substrate. Further, as Comparative Example 3, the surface treatment film was not formed, but the glass substrate itself was used. Further, as Comparative Example 4, heptadecafluoro-1,1,2,2-tetrahydroindenyltriethoxy group was formed on a glass substrate in accordance with the method described in Example 1 of JP-A-2004-6700. Surface treatment film of decane.

<Evaluation method of surface treatment film>

1) Contact angle measurement

The ink repellency of the obtained surface-treated film or glass substrate was measured by using DropMaster 500 manufactured by Kyowa Interface Chemical Co., Ltd. at 25 ° C to measure a (meth)acrylic monomer which is often used as a constituent component of the ink for inkjet. The contact angle of 2-hydroxyethyl methacrylate (HEMA) and cyclohexyl methacrylate (CH) was evaluated. The value after the droplet was attached for 1 second was taken as the contact angle.

2) Descriptive evaluation

Using a (meth)acrylic monomer, 2-hydroxyethyl methacrylate (HEMA) and cyclohexyl methacrylate (CH), the inkjet method was used for drawing on a surface treated film or a substrate, and the evaluation was performed. The difference in the width of the formed line pattern film caused by the type of the surface treatment agent and the presence or absence of the surface treatment.

(Inkjet drawing conditions)

Printing device: DMP-2831 (trade name: manufactured by FUJIFILM Dimatix Co., Ltd.)

Setting values: head temperature (30 ° C), piezoelectric voltage (19 V), drive frequency (5 kHz), nozzle (10 pL)

Coating: Disposable coating.

3) Alkali solubility

a glass substrate surface-treated with a surface treatment agent or heptadecanefluro-1,1,2,2-tetrahydroindenyltriethoxydecane prepared in the formation of the surface treatment film, After immersing in a 0.4 wt% TMAH aqueous solution at 25 ° C for 60 seconds, the glass substrate was taken out, rinsed with ultrapure water, dried, and then the contact angle of pure water at 25 ° C on the surface of the substrate was measured to confirm whether or not the glass substrate was removed. A surface treatment film. It is determined that AA is determined if the contact angle is less than 50 degrees, and BB is determined if the contact angle is 50 degrees or more.

The above evaluation results are shown in Table 1 below.

[Table 1]

As shown in Table 1, the surface comprising a copolymer having a structural unit derived from a specific compound containing ruthenium, a structural unit derived from a radical polymerizable monomer having a hydrophilic group, and a solvent The film formed by the treating agent (surface treatment film) can improve the contact angle of HEMA or CH which is often used in the inkjet ink with respect to the substrate, and can be applied to the substrate by inkjet method (specifically, the surface treatment film) ) Forming a fine patterned film. Further, it is understood that the surface treatment film has high solubility in an alkali solution and can be easily removed. Further, the surface treatment agent of the present invention can form a surface treatment film of the same level as the prior art (Japanese Patent Laid-Open No. 2004-6700, etc.) in a simple and rapid manner.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Claims (9)

A surface treatment agent for imparting ink repellency to a substrate, characterized in that it comprises: a copolymer, wherein the copolymer has a 3-methacryloxypropyltris(trimethyldecyloxy)decane or a structural unit derived from the compound (a) represented by the following formula (3) and a structural unit derived from a radical polymerizable monomer (b) having a hydrophilic group; and a solvent (e): In the formula (3), R ⁹ is an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 1000. The surface treatment agent according to claim 1, wherein the hydrophilic group in the radical polymerizable monomer (b) is a hydroxyl group, a carboxyl group or a phenolic hydroxyl group. The surface treatment agent according to claim 1, wherein the copolymer further has a structural unit derived from a radical polymerizable monomer (c) other than the radical polymerizable monomer (b) . The surface treatment agent according to claim 1, wherein the radical polymerizable monomer (b) is (meth)acrylic acid or 4-hydroxyphenylvinylketone. The surface treatment agent according to claim 3, wherein the radical polymerizable monomer (c) is N-phenylmaleimide, dimethylaminoethyl (meth)acrylate or Butyl (meth)acrylate. A method of imparting ink repellency to a substrate, comprising the step of forming a surface treatment film on a substrate using a surface treatment agent as described in claim 1. A method of forming a pattern film by forming a pattern film having a width of 200 μm or less on a substrate to which ink repellent property is imparted by the inkjet coating method according to the method of claim 6 method. An electronic component having a patterned film formed by the method of claim 7 of the patent application. A method of producing an electronic component, comprising the step of forming a surface treatment film on a substrate using the surface treatment agent according to claim 1 of the patent application, and forming a solid film or a pattern film on the surface treatment film.