JP2018076446A - Soluble polyfunctional vinyl copolymer method for producing the same, curable resin composition containing the same, and coated film and cured product of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new soluble polyfunctional vinyl copolymer having improved heat resistance, adhesion, mutual solubility, gas barrier properties, dispersibility and flexibility; a method for producing the same; and a coating liquid using an aqueous solvent using the same.SOLUTION: There are provided a soluble polyfunctional vinyl copolymer which is obtained by copolymerization of a bifunctional (meth)acrylate compound having (meth)acrylic acid and a hydroxyl group and monomers containing a thiol compound having a carboxyl group, satisfies a structural unit (b1) having a reactive (meth)acrylate group derived from a bifunctional (meth)acrylic compound having a hydroxyl group in its side chain, has a structural unit (c) derived from a thiol compound having a carboxyl group in its terminal, has a number average molecular weight Mn of 500-5,000,000, and is soluble in methanol, ethanol, isopropanol or tetrahydrofuran; and a water soluble polyfunctional vinyl copolymer obtained by neutralization of the same.SELECTED DRAWING: None

Description

  The present invention relates to a novel soluble polyfunctional vinyl copolymer having improved heat resistance, adhesiveness, compatibility, gas barrier properties, dispersibility and flexibility, a method for producing the same, a curable resin composition containing the same, and a filler Are uniformly dispersed and a low-odor solvent or water-based filler-dispersed curable resin composition that enables formation of a conductive coating film with a low environmental load, its coating film, and a cured product thereof, and It relates to their utilization technology.

  In recent years, a dispersion liquid or paste containing a functional material (hereinafter also referred to as a slurry) is used as a coating liquid, and an attempt is made to use the functionality of a coating film formed by applying this coating liquid. Has been studied in various fields.

  For example, a paste-like conductive coating liquid composed of a conductive filler, a binder resin, a curing agent, a solvent, and the like is used as a conductive adhesive, a conductive paint, a conductive ink, and the like (Non-Patent Document 1). . Also, for coating-type magnetic recording media such as audio tapes, video tapes, and floppy disks, a magnetic paint in which submicron-sized magnetic particles are uniformly dispersed in a polymer solution is applied to a base film such as polyester. It is made by. Furthermore, a titanium oxide photocatalyst is highly dispersed using a dispersant, and a titanium oxide coating solution composed of a binder resin, a curing agent, a solvent, etc., a photocatalyst coating film and a photocatalyst-coated body formed using this coating solution are Since it exhibits a strong oxidizing action when it absorbs ultraviolet rays, it has recently been used as a photocatalyst in various applications such as air purification, deodorization, water purification, antibacterial, and antifouling. (Patent Documents 1 to 3).

The common attribute that the various coating liquids as described above can sufficiently exhibit their functionality is that the dispersoid is uniformly dispersed in the dispersion medium, and the formed coating film achieves high adhesion. It is. In other words, in order to fully develop the functionality of the filler in the slurry containing the functional filler, the state of the slurry is appropriate for the expression of the functionality, that is, the filler is uniformly and stably dispersed. In addition, it is essential to be able to form a coating film with high adhesion. For this purpose, first, considering an appropriate solvent centering on the dispersibility of the filler, the slurry solvent (dispersion medium) is excellent in uniform dispersibility of the filler, exhibits high adhesion, and is easy to dry. A non-aqueous organic solvent is overwhelmingly advantageous and has been widely used in practice.
However, organic solvents are not only volatile and have a large environmental impact, but also have to consider genotoxicity, leaving problems in safety and workability. In recent years, awareness of environmental protection and health damage prevention has been increasing in many industrial fields, and there is an increasing demand for VOC reduction and solvent-free use of organic solvents with the above-mentioned problems. There is a need to shift to products that are friendly to the environment and people.

  Therefore, the most noticeable products that are friendly to the environment and health are products made of water-based products or biological materials, and are expected to play a part in solvent-free or petroleum-free products. However, in a conductive carbon filler-containing slurry or the like, various problems arise when water is used as a solvent instead of an organic solvent. For example, in an aqueous slurry, when the filler particles are in a charged state, the particles are likely to aggregate in the slurry, and further, because the specific gravity difference between the solvent and the solute is large, the particles are likely to settle, and uniform dispersion is very difficult. is there. In addition, it is not easy to find a bio-derived raw material that exhibits coating film forming ability and dispersibility that can be substituted for conventional petroleum-derived raw materials.

  Here, as a general countermeasure for poor dispersion, addition of a dispersant, surface treatment of a filler, microencapsulation, ultrasonic treatment, introduction of a polar group into a polymer, and the like can be considered. As a dispersant addition, an attempt to use a water-soluble amphoteric dispersant for a slurry composition containing finely divided black inorganic oxide used in paints, inks, rubber / plastics, electronic materials, etc. (patented) There is an attempt to use a compound having a basic functional group in Patent Document 4) and a battery composition containing a conductive additive (Patent Document 5). Various filler surface treatments such as an attempt to form a surface treatment layer by reacting the metal oxide on the surface of the metal oxide fine particle filler with a hydrophilic silane coupling agent have been proposed (Patent Document 6). Other proposals such as applying ultrasonic vibration to paste containing inorganic oxide filler to disperse the filler, or forming insulating resin on the surface of conductive filler to make microcapsule type conductive filler There is also.

  However, an organic solvent is mainly used as a dispersion medium used in these attempts, and there are very few examples using an aqueous solvent. On the other hand, due to the recent increase in awareness of environmental protection and health damage prevention, the emergence of methods that use environmentally friendly and highly safe water-based slurries and evenly distribute functional fillers is strongly desired. Yes.

  When trying to stabilize the dispersion of the filler in the aqueous slurry, the above-mentioned methods can be considered, but the use of an aqueous binder resin is advantageous in view of simplification of the manufacturing process and coating system and cost. As the binder resin used in the aqueous slurry, a polycarboxylic acid salt, a cellulose resin (Non-Patent Document 2), a polyacrylic acid amide (Non-Patent Document 3) and the like used in the paint field are considered. A binder resin having a hydrogen bonding site can also provide excellent weather resistance and gas barrier properties reflecting the strength of intermolecular interaction between main chains.

  As an expected use of the above aqueous slurry composition, a coating solution for an electrode plate of a power storage device such as a secondary battery or a capacitor, which has been growing remarkably in recent years, can be considered. The electrode plate has a great influence on the performance of the power storage device, and is an electrode member in which unit members such as an electrode layer and a current collector are integrated. However, with respect to the electrode plate, the charge / discharge cycle life is extended and high performance is achieved. It has been proposed to increase the area of the thin film in order to increase the energy density. For example, as described in Patent Document 7 and Patent Document 8 for lithium ion batteries, a positive electrode active material powder such as a metal oxide, sulfide, halide, etc., a conductive material and a binder in an appropriate solvent. Disperse and dissolve to prepare a paste-like coating liquid, and use a current collector made of a metal foil such as aluminum as a base, and apply the coating liquid on the surface of the base to form a coating film layer. A positive electrode plate is disclosed.

Capacitors that use an electric double layer formed at the interface between a polarizable electrode plate and an electrolyte are used as memory backup power supplies, and are also attracting attention for applications that require high output such as power supplies for electric vehicles. For output, both high capacitance and low internal resistance are required. The electrode plate for a capacitor is generally manufactured by applying and drying a coating solution, which is a mixture of a binder and a conductive material, on a current collector, like the negative electrode plate of the battery.
However, the binder resins as described above have problems in flexibility and heat resistance when considering use in various industrial products, and have problems in environmental reliability at high temperatures.

JP 2007-252987 A JP 2009-056348 A JP 2010-222444 A JP 2009-148681 A JP 2009-26744 A JP 2008-184485 A Special table 2015-535643 gazette JP-A-3-285262

Harunori Goji, Takafumi Imai, Akihiro Wakahara: “Chapter 3, Selection and Mixing of Dispersants According to Purpose and Countermeasures for Problems with Dispersants”, “Latest Pigment Dispersion Know-how Collection” Technical Information Association, pages 69-105, 2008 Kiyokazu Shiro: "Technological development of dispersant for water-based paint", JETI, Vol. 44, No. 10, pp. 110-112, 1996 Hidehiro Kamiya: “Evaluation and Control of Aggregation and Dispersion Behavior of Fine Particles in Water System”, Material stage, Vol. 2, No. 1, pp. 54-60, 2002

Therefore, the object of the present invention is to solve the above-mentioned problems and to have an excellent dispersing function for a functional filler while being a material suitable for an aqueous slurry having a low environmental load, and also an excellent function as a binder. To provide a binder resin capable of forming a functional coating film having an excellent balance of adhesion, heat resistance and flexibility, and to provide an aqueous functional filler-dispersed coating liquid is there. More specifically, an object of the present invention is to provide an aqueous functional filler-dispersed coating liquid that maintains viscosity even when stored for a long period of time, does not easily cause sedimentation and separation of the functional filler, and has high dispersibility. If such a coating liquid is provided, it becomes possible to form a highly functional coating film with excellent adhesion obtained by uniformly dispersing the functional filler, so that it is possible to form an electronic material paint, ink, toner, rubber. -Expected to be used in various fields such as plastics, ceramics, magnetic materials, adhesives, liquid crystal color filters, and batteries. An object of the present invention is to provide a technology that can be used in many industrial fields that can contribute to environmental protection and health damage prevention, which are social problems.
From this point of view, the present invention provides a novel soluble polyfunctional vinyl copolymer with improved heat resistance, adhesion, compatibility, gas barrier properties, dispersibility and flexibility, its production method and filler uniformly dispersed. An object of the present invention is to provide an aqueous filler-dispersed curable resin composition, a coating film thereof, and a cured product that enable formation of a conductive coating film with less environmental load.

  As a result of intensive studies, the inventors have obtained a specific copolymer obtained by copolymerizing a component containing (meth) acrylic acid and a bifunctional (meth) acrylic acid having a hydroxyl group and a thiol compound having a carboxyl group. It has been found that a copolymer or a neutralized product thereof can solve the above-mentioned problems, and the present invention has been completed.

（ここで、式中、Ｒ^２及びＲ^５は、それぞれ独立して水素原子又はメチル基を示し、Ｒ^３及びＲ^４は、それぞれ独立して炭素数１〜１０のアルキレン基を示す。）
及びカルボキシル基を有するチオール化合物に由来する構造単位（ｃ）を有する共重合体であって、
構造単位（ｂ）の少なくとも一部は共重合体の鎖中に存在する反応性の（メタ）アクリレート基を含有する構造単位（ｂ１）であり、構造単位（ｂ１）のモル分率が下記式（３）を満足すること、構造単位（ｃ）を末端に有し、構造単位（ｃ）のモル分率が下記式（４）を満足すること、
（ｂ１）／［（ａ）＋（ｂ）］≧０．００５ （３）
０．００１≦（ｃ）／［（ａ）＋（ｂ）＋（ｃ）］≦０．５ （４）
（式（３）、式（４）において、（ａ）、（ｂ）、（ｃ）及び（ｂ１）は、それぞれ構造単位（ａ）、（ｂ）、（ｃ）及び（ｂ１）の存在量（モル）を示す。）
及び前記共重合体の数平均分子量Ｍｎが１０００〜２，０００，０００であり、分子量分布が５００．０以下であり、メタノール、エタノール、イソプロパノール又はテトラヒドロフランに可溶であることを特徴とする水酸基とカルボキシル基を有する可溶性多官能ビニル共重合体である。 The present invention includes a structural unit (a) derived from (meth) acrylic acid, a structural unit (b) derived from a bifunctional (meth) acrylate compound having a hydroxyl group represented by the following formula (2),

(Wherein, R ² and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ³ and R ⁴ each independently represent an alkylene group having 1 to 10 carbon atoms.)
And a copolymer having a structural unit (c) derived from a thiol compound having a carboxyl group,
At least a part of the structural unit (b) is a structural unit (b1) containing a reactive (meth) acrylate group present in the copolymer chain, and the molar fraction of the structural unit (b1) is represented by the following formula: Satisfying (3), having the structural unit (c) at the terminal, and the molar fraction of the structural unit (c) satisfying the following formula (4);
(B1) / [(a) + (b)] ≧ 0.005 (3)
0.001 ≦ (c) / [(a) + (b) + (c)] ≦ 0.5 (4)
(In the formulas (3) and (4), (a), (b), (c) and (b1) are the abundances of the structural units (a), (b), (c) and (b1), respectively. (Mol).)
And a hydroxyl group characterized in that the copolymer has a number average molecular weight Mn of 1000 to 2,000,000, a molecular weight distribution of 500.0 or less, and is soluble in methanol, ethanol, isopropanol or tetrahydrofuran It is a soluble polyfunctional vinyl copolymer having a carboxyl group.

  The present invention also includes copolymerizing monomers including (meth) acrylic acid, a bifunctional (meth) acrylate compound having a hydroxyl group represented by the above formula (2), and a thiol compound having a carboxyl group. This is a method for producing the above-mentioned soluble polyfunctional vinyl copolymer.

  Furthermore, the present invention provides a water-soluble polyfunctional vinyl copolymer characterized in that at least a part of the COOH group of the above-mentioned soluble polyfunctional vinyl copolymer is COOM (M is an alkali metal or ammonium). is there. The present invention also provides a method for producing the water-soluble polyfunctional vinyl copolymer described above, wherein the soluble polyfunctional vinyl copolymer is neutralized with an alkali.

  Moreover, this invention is a curable resin composition characterized by containing said soluble polyfunctional vinyl copolymer (A), an initiator (B), and a solvent (C). This curable resin composition can be a filler-containing curable resin composition containing a filler (D) or a filler (D) and a thickener (E).

  The present invention also provides a curable resin composition comprising the water-soluble polyfunctional vinyl copolymer (A1), an initiator (B), and an aqueous solvent (C1). This curable resin composition can be a filler-containing curable resin composition containing a filler (D) or a filler (D) and a thickener (E).

  Furthermore, the present invention is a cured product of any one of the above curable resin compositions, a coating film comprising the curable resin composition, or a cured product thereof.

The soluble polyfunctional vinyl copolymer of the present invention is a material suitable for an aqueous slurry having a low environmental load or an intermediate thereof, and has an excellent dispersing function for a functional filler, and is also excellent as a binder. It shows the function and enables the formation of a functional coating film with excellent balance of adhesion, heat resistance and flexibility. Moreover, the viscosity of the curable resin composition or filler-containing curable resin composition blended therewith is maintained even if stored for a long period of time, and the functional filler does not easily precipitate and separate. And, since it becomes possible to form a highly functional coating film with excellent adhesion obtained by uniformly dispersing the functional filler, electronic material paint, ink, toner, rubber / plastic, ceramic, magnetic substance, adhesive It can be expected to be used in various fields such as liquid crystal color filters and batteries.
The soluble or water-soluble polyfunctional vinyl copolymer of the present invention, a curable resin composition containing the same, or a coating film produced from the filler-dispersed curable resin composition or a cured product thereof has heat resistance, adhesiveness, Compatibility, dispersibility and flexibility are improved. Moreover, according to the production method of the present invention, the copolymer can be produced with high efficiency. In addition, by using the water-soluble polyfunctional vinyl copolymer of the present invention as a binder resin, it has an excellent dispersion function for functional fillers while being a material suitable for an aqueous slurry with a low environmental load. Moreover, it exhibits an excellent function as a binder, and can form a functional coating film having an excellent balance of adhesion, heat resistance and flexibility.

  Although the manufacturing method of the soluble polyfunctional vinyl copolymer of this invention is not limited, A (meth) acrylic acid compound and the bifunctional (meth) acrylate compound which has a hydroxyl group represented by said Formula (2) And a method of copolymerizing monomers containing a carboxyl group-containing thiol compound is suitable. Hereinafter, the soluble polyfunctional vinyl copolymer of the present invention may be described using monomers used in the production method, but this is understood for convenience.

The soluble polyfunctional vinyl copolymer includes a structural unit (a) derived from a (meth) acrylic acid compound and a structural unit derived from a bifunctional (meth) acrylate compound having a hydroxyl group represented by the above formula (2) ( b) and a copolymer having a structural unit (c) derived from a thiol compound having a carboxyl group, and at least a part of the structural unit (b) is a reactive (meta) present in the chain of the copolymer. ) A structural unit (b1) containing an acrylate group, the molar fraction of the structural unit (b1) satisfies the above formula (3), has the structural unit (c) at the terminal, and the structural unit (c) The molar fraction satisfies the above formula (4).
The soluble polyfunctional vinyl copolymer of the present invention is also referred to as a copolymer when it does not cause misunderstanding.

  The soluble polyfunctional vinyl copolymer of the present invention has the structural units (a), (b) and (c). The structural unit (b) is derived from a bifunctional (meth) acrylate compound having a hydroxyl group represented by the above formula (2). Since the bifunctional (meth) acrylate compound has two polymerizable (meth) acrylate groups, it is crosslinked and polymerized to give a cured resin. ) Having a structural unit in which only one of the acrylate groups is involved in the polymerization and a structural unit in which both are involved in the polymerization. A structural unit in which both are involved in polymerization forms a branched chain and contributes to a multi-branched structure.

At least a part of the structural unit (b) exists as a structural unit (b1) containing a reactive (meth) acrylate group in the chain. Since this structural unit (b1) has polymerizability, it gives crosslinking and curability to the copolymer.
The abundance of the structural unit (b1) satisfies the above formula (3). Preferably, the molar fraction represented by Formula (3) is 0.01 to 0.9, and more preferably 0.02 to 0.8. When the molar fraction is less than 0.01, the heat resistance and flexibility of the cured product produced by curing the copolymer are lowered.

The structural unit (c) is derived from a thiol compound having a carboxyl group, but since it does not have a polymerizable group, it acts as a chain transfer agent and is present at a part or all of the terminals.
The abundance of the structural unit (c) satisfies the above formula (4). That is, the molar fraction of the structural unit (c) is in the range of 0.001 to 0.5 with respect to the total (mole) of the structural units (a), (b) and (c), preferably 0. The range is 0.002 to 0.4.
When the molar fraction is less than 0.001, the molecular weight of the copolymer increases and the moldability decreases. On the other hand, if it exceeds 0.5, the molecular weight of the copolymer is lowered, so that the dispersion stability of the filler is lowered and the heat resistance of the cured product is lowered.

The soluble polyfunctional vinyl copolymer of the present invention has the above structural units (a), (b) and (c), and the abundance of each of the structural units (a) and (b) is the structural unit (a). And (b), the following molar fraction is preferably satisfied with respect to the total (mole).
The molar fraction of the structural unit (a) is 0.2 to 0.995, preferably 0.25 to 0.99, when calculated by (a) / {(a) + (b)}. Preferably it is the range of 0.30-0.98 mol.
The mole fraction of the structural unit (b) is calculated from the mole fraction of the structural unit (a) when calculated by (b) / {(a) + (b)}. From another viewpoint, it is preferable that the structural unit (a) is contained in an amount of 20 to 99.5 mol% with respect to 100 mol% in total of all the structural units.
Since the structural unit (b) has a hydroxyl group and a (meth) acrylic acid group, it has heat resistance and an effect of suppressing excessive aggregation of the structural unit (a). On the other hand, the structural unit (a) derived from monofunctional (meth) acrylic acid provides adhesion, compatibility, dispersibility, moldability, and the like. Accordingly, when the molar fraction of the structural unit (b) is less than 0.005, the heat resistance of the cured product is insufficient, and when it exceeds 0.8, the moldability is deteriorated.

  The number average molecular weight Mn (standard polystyrene equivalent number average molecular weight measured using gel permeation chromatography) of the soluble polyfunctional vinyl copolymer of the present invention is 1,000 to 2,000,000, preferably 2, 000 to 1,000,000. When the Mn is less than 1,000, the amount of the monofunctional copolymer contained in the copolymer increases, so that the heat resistance and toughness of the cured product is reduced, and the Mn exceeds 2,000,000. Then, the gel is easily generated and the viscosity becomes high, so that the molding processability is lowered. The value of the molecular weight distribution (Mw / Mn) represented by the ratio between the weight average molecular weight Mw and Mn is 100.0 or less, preferably 1.5 to 70.0. More preferably, it is 2.0-40.0. When Mw / Mn exceeds 100.0, problems such as deterioration of the processing characteristics of the copolymer and generation of a gel occur.

  The soluble polyfunctional vinyl copolymer of the present invention is soluble in one or more solvents selected from the group consisting of methanol, ethanol, isopropanol, and tetrahydrofuran, but is preferably soluble in any of the above solvents. is there. Here, “soluble in a solvent” means that 5 g or more, preferably 10 g or more is dissolved in 100 g of a solvent at 25 ° C. In order to be a polyfunctional copolymer that is soluble in a solvent, a part of the (meth) acrylic acid group of the bifunctional (meth) acrylic acid compound (b) having a hydroxyl group is allowed to remain without crosslinking. It is necessary that the degree of crosslinking is moderate. The polymerization method will be described later.

  Since the structural units (a) and (c) in the soluble polyfunctional vinyl copolymer of the present invention have a carboxyl group, they can be dissolved in water by partially neutralizing or completely neutralizing them. Can be improved. By using such a neutralized copolymer, it is possible to prepare an aqueous slurry in which a functional filler is dispersed in a region close to neutrality, and it is excellent in dispersibility, dispersion stability, and coatability. Functional filler dispersions can be provided. Even if neutralization is performed, other structures of the copolymer are maintained.

  Next, the manufacturing method which can manufacture the soluble polyfunctional vinyl copolymer of this invention advantageously is demonstrated.

  As the raw material monomers, (meth) acrylic acid, a bifunctional (meth) acrylate compound having a hydroxyl group represented by the formula (2), and a thiol compound having a carboxyl group are used.

  Examples of (meth) acrylic acid include, but are not limited to, acrylic acid, methacrylic acid, α-ethylacrylic acid, and the like. Acrylic acid or methacrylic acid is preferred from the viewpoint of cost and availability in order to prevent gelation of the copolymer and improve solubility in solvents, adhesion, dispersibility of fillers, and processability. Used.

The bifunctional (meth) acrylate compound having a hydroxyl group represented by the formula (2) branches the copolymer to relieve the cohesive force of the copolymer and to make the copolymer polyfunctional. It plays an important role as a cross-linking component for developing heat resistance when thermosetting.
In Formula (2), R ² and R ⁵ each independently represent a hydrogen atom or a methyl group. R ³ and R ⁴ each independently represent an alkylene group having 1 to 10 carbon atoms.
Examples of the bifunctional (meth) acrylic acid compound (b) are not limited as long as they satisfy the formula (2). However, from the viewpoint of molding processability, 2-hydroxy-3-acrylic acid compound (b) is not limited. Leuoxypropyl methacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, glycerin diacrylate, 4-hydroxy-3-acryloyloxybutyl methacrylate, 4-hydroxy-3-acryloyloxybutyl acrylate, di Glycerin dimethacrylate and the like are preferably used. Moreover, these can be used individually or in combination of 2 or more types. More preferred is 2-hydroxy-3-acryloyloxypropyl methacrylate.

  The thiol compound having a carboxyl group plays an important role as a component that prevents gelation of the copolymer and improves solubility in a solvent, adhesion, dispersibility of a filler, and processability. Specific examples of the thiol compound having a carboxyl group include thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, 2-mercaptoisobutyric acid, 3-mercaptoisobutyric acid, 3-mercapto- Specific examples include 3-methylbutyric acid, 2-mercaptovaleric acid, 3-mercaptoisovaleric acid, 4-mercaptovaleric acid, 3-phenyl-3mercaptopropionic acid, mercaptobenzoic acid, and the like. is not. In particular, thioglycolic acid, 2-mercaptopropionic acid, and 3-mercaptopropionic acid are used to prevent the gelation of the copolymer and improve solubility in solvents, adhesiveness, dispersibility of fillers, and processability. Is preferred from the viewpoint of cost and availability.

（ここで、Ｒ^２及びＲ^５は、それぞれ独立して水素原子又はメチル基を示し、Ｒ^３及びＲ^４は、それぞれ独立して炭素数１〜１０のアルキレン基を示す。ｍ、ｎ、ｏ及びｐは、それぞれ独立に１以上であり、かつ共重合体としての数平均分子量Ｍｎが１０００〜２００００００であり、分子量分布が１００．０以下となる整数を表す。） An example of a reaction in which a thiol compound having a carboxyl group is inserted at the end of the copolymer is shown below.

(Here, R ² and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ³ and R ⁴ each independently represent an alkylene group having 1 to 10 carbon atoms. M, n, o And p are each independently an integer of 1 or more, a number average molecular weight Mn as a copolymer of 1,000 to 2,000,000, and a molecular weight distribution of 100.0 or less.)

  In addition, in the copolymer production method, in addition to the bifunctional (meth) acrylate compound having a hydroxyl group represented by (meth) acrylic acid and the general formula (2) as long as the effects of the present invention are not impaired, Others such as monovinyl aromatic compounds, divinyl aromatic compounds, trivinyl aromatic compounds, trivinyl aliphatic compounds, divinyl aliphatic compounds, monovinyl aliphatic compounds, monofunctional (meth) acrylic acid esters, bifunctional (meth) acrylic acid esters, etc. The monomer (e) can be used to introduce this unit into the copolymer.

  Specific examples of the other monomer (e) include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diacrylate. , Butadiene, isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxy Ethyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, cyclohexane dimethanol diacrylate, dimethylol tricyclodecane diacrylate, cyclohexane dimethanol dimethacrylate, dimethyl Tricyclodecane dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butane Examples include diol dimethacrylate, hexanediol dimethacrylate, and diethylene glycol dimethacrylate, but are not limited thereto. These can be used alone or in combination of two or more. The other monomer (e) may be used within a range of less than 30 mol% of the total monomers. Thereby, the structural unit derived from the other monomer component (e) is within a range of less than 30 mol% with respect to the total amount of the structural unit in the copolymer.

In the method for producing a soluble polyfunctional vinyl copolymer of the present invention, a radical polymerization initiator can be added when the initiation reaction rate by the thermal initiation reaction is low. Examples of radical polymerization initiators in this case include ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy)- Peroxyketals such as 3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate; cumene hydroper Hydroperoxides such as oxide, 2,5-dimethylhexane-2,5-dihydroperoxide; 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2, 5-di (tert-butylperoxy) hexane, diisopropyl Dialkyl peroxides such as benzene peroxide and tert-butylcumyl peroxide; diacyl peroxides such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide and 2,4-dichlorobenzoyl peroxide; bis (tert-butyl Peroxycarbonates such as cyclohexyl) peroxydicarbonate; organic peroxides such as peroxyesters such as tert-butylperoxybenzoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane Polymerization initiator and 2,2′-azobisisobutyronitrile, 1,1-azobis (cyclohexane-1-carbonitrile), azocumene 2,2′-azobismethylvaleronitrile, 4,4′-azobis (4 -Azo polymerization initiators such as cyanovaleric acid) Can. The amount of these radical polymerization initiators used is not particularly limited, but it is usually preferably 0.01 to 25 parts by weight based on 100 parts by weight of the total amount of monomers. More desirably, it is in the range of ˜20 parts by weight. Most preferably, it is in the range of 0.1 to 15 parts by weight.
The polymerization reaction can be carried out by bulk polymerization without using a solvent, but is basically carried out in one or more organic solvents that dissolve the soluble polyfunctional vinyl copolymer produced. The organic solvent is a compound that does not essentially inhibit radical polymerization, and dissolves the chain transfer agent, initiator, monomer, and polyfunctional (meth) acrylate aromatic copolymer of the present invention, and is homogeneous. If it forms a solution, it can be used without particular limitation.

  Examples of compounds that can be used as organic solvents include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; acetone, 2-butanone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl Ketones such as isobutyl ketone, cyclopentanone and cyclohexanone; esters such as ethyl acetate, propyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; benzene, toluene, Aromatic hydrocarbons such as xylene, ethylbenzene, propylbenzene, butylbenzene and the like can be mentioned. Among these, 2-propanol, 1-butanol, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, and xylene are preferable. 2-Propanol, 1-butanol, 2-butanone, and methyl ethyl ketone are more preferable from the viewpoints of a balance between polymerizability and solubility and availability.

  These compounds are used alone or in combination of two or more. There is no restriction | limiting in particular in the usage-amount of a solvent.

  The polymerization reaction is preferably performed by reacting the above-described components containing the monomers in the presence of a solvent having a dielectric constant of 2.0 to 15.0 at a temperature of 20 to 120 ° C., thereby having a hydroxyl group and a carboxyl group. A polyfunctional vinyl copolymer can be produced.

  The polymerization reaction is preferably carried out in one or more organic solvents having a dielectric constant of 2 to 15 as a solvent for dissolving the produced soluble polyfunctional vinyl copolymer. The organic solvent is a compound that does not essentially inhibit radical polymerization, and dissolves an initiator, a polymerization additive, a monomer, and a soluble polyfunctional vinyl copolymer to form a uniform solution. If a dielectric constant is in the range of 2-15, there will be no restriction | limiting in particular, It can use individually or in combination of 2 or more types. If the dielectric constant of the solvent is less than 2, it is not preferable because the solubility in the soluble polyfunctional vinyl copolymer is lowered, and if it exceeds 15, the polymerization rate is significantly reduced.

  The amount of the solvent used is 1 to 90 wt%, preferably 10 to 80 wt%, especially the concentration of the copolymer in the polymerization solution at the end of the polymerization in consideration of the viscosity of the resulting polymerization solution and the ease of heat removal. Preferably, it is determined to be 20 to 70 wt%. If this concentration is less than 1 wt%, the polymerization efficiency is low, resulting in an increase in cost. If it exceeds 90 wt%, the molecular weight and molecular weight distribution increase, resulting in a decrease in molding processability.

  The polymerization reaction temperature is preferably 20 to 120 ° C, more preferably 40 to 100 ° C. If the polymerization temperature is too high, the selectivity of the reaction will decrease, causing problems such as an increase in molecular weight distribution and gel generation. If it is too low, the polymerization rate will be significantly reduced, so a large amount of initiator must be added. Occurs.

  The method for recovering the copolymer after the termination of the polymerization reaction is not particularly limited. For example, a commonly used method such as devolatilization, steam stripping, or precipitation with a poor solvent may be used.

The soluble polyfunctional vinyl copolymer of the present invention is soluble in an organic solvent as described above. However, a part or all of the carboxyl group may be an alkali metal such as lithium, sodium, potassium, cesium, or ammonia. It is preferable to obtain a water-soluble polyfunctional vinyl copolymer that is neutralized with an alkali and has improved solubility in water.
By neutralizing a part or all of the carboxyl groups of the soluble polyfunctional vinyl copolymer of the present invention, water solubility can be increased, so water or a mixed solvent in which the proportion of water is increased (aqueous solvent) Can be used, and a curable resin composition with less environmental load can be obtained.

Next, the curable resin composition of the present invention will be described.
The curable resin composition of the present invention comprises a soluble polyfunctional vinyl copolymer (A) having a hydroxyl group and a carboxyl group of the present invention or a water-soluble polyfunctional vinyl copolymer (A1), an initiator (B), and It contains a solvent (C) or an aqueous solvent (C1). In the following description, when there is no need to distinguish between the soluble polyfunctional vinyl copolymer (A) and the water-soluble polyfunctional vinyl copolymer (A1), the soluble polyfunctional vinyl copolymer (A) is represented by the soluble polyfunctional vinyl copolymer (A). When there is no need to distinguish between the solvent (C) and the aqueous solvent (C1), it is represented by the solvent (C).

  As the initiator (B), for example, the resin composition of the present invention is cured by causing a crosslinking reaction by means of heating or the like as will be described later. For the purpose of accelerating the crosslinking reaction, a radical polymerization initiator (B) may be contained and used. The amount of the radical polymerization initiator used for this purpose is 0.01 to 10% by weight, preferably 0.1 to 8% by weight, based on the component (A). Since the radical polymerization initiator is a radical polymerization catalyst, it is represented below by a radical polymerization initiator.

  A known substance is used as the initiator. As typical examples, for example, ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3, Peroxyketals such as 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate; cumene hydroperoxide, Hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide; 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5- Di (tert-butylperoxy) hexane, diisopropylbenzenepero Dialkyl peroxides such as side, tert-butylcumyl peroxide; diacyl peroxides such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide; bis (tert-butylcyclohexyl) Peroxycarbonates such as peroxydicarbonate; organic peroxide polymerization such as tert-butylperoxybenzoate, peroxyesters such as 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, etc. Agent, and 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrochloride, dimethyl 2,2′-azobis Isobutyrate, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-acrylate Zobis (2-methylbutyronitryl), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis {2-methyl-N- [2- (1-hydroxybutyl)] propionamide }, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis [2- ( 5-methyl-2-imidazolin-2-yl) propane] hydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2'-azobis [2- ( 2-imidazolin-2-yl) propane] sulfate, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] hydrochloride, 2,2'-azobis { 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} hydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2 ′ -Azobis (2-methylbutanamidoxime) dihydrochloride and 1,1'-azobis (1-acetoxy-1-phenyl) ) Azo-based polymerization initiator such as ethane may also be mentioned. Furthermore, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical polymerization initiator (or polymerization catalyst).

In the curable resin composition of the present invention, water, an organic solvent, or a mixed solvent thereof can be used as the solvent (C). The aqueous solvent (C1) is water or a mixed solvent of water and an organic solvent.
Examples of the organic solvent include methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, diacetone alcohol, furfuryl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, alcohols such as glycerin; esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate; diethyl ether, diisopropyl ether, dibutyl ether , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, die Glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, chain or cyclic ethers such as dioxane; acetone, methyl ethyl ketone, acetylacetone, and the like ketones such as ethyl acetoacetate. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

  If necessary, the curable resin composition of the present invention may be mixed with another polymerizable monomer copolymerizable with the copolymer (A) and cured.

  A known substance is used as such a copolymerizable polymerizable monomer. Typical examples include monovinyl aromatic compounds, divinyl aromatic compounds, trivinyl aromatic compounds, trivinyl aliphatic compounds, divinyl aliphatic compounds, monovinyl aliphatic compounds, monofunctional (meth) acrylic acid esters, bifunctional ( Other monomers (e) such as (meth) acrylic acid esters can be mentioned.

  In the curable resin composition of the present invention, a known thermosetting resin such as a vinyl ester resin, a polyvinyl benzyl resin, an unsaturated polyester resin, a curable vinyl resin, a modified polyphenylene ether resin, a maleimide resin is used as necessary. , Epoxy resins, polycyanate resins, phenol resins, etc., known thermoplastic resins such as polystyrene, polyphenylene ether, polyether imide, polyether sulfone, PPS resin, polycyclopentadiene resin, polycycloolefin resin, or the like Known thermoplastic elastomers such as styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, Hydrogenated violet - isoprene copolymer and or gums such as polybutadiene, may be blended with polyisoprene.

The curable resin composition of this invention can contain a filler (D) as the one aspect | mode. A curable resin composition containing a filler is also referred to as a filler-containing curable resin composition.
Fillers (D) include silver, copper, aluminum, iron, stainless steel, nickel, gold, zinc, nickel, tin, lead, chromium, platinum, palladium, tungsten, molybdenum, tantalum, niobium, titanium, hafnium, zirconium, Metal fillers such as zinc, tungsten, bismuth, antimony, platinum, magnesium oxide (MgO), aluminum oxide (Al ₂ O ₃ ), boron nitride (BN), aluminum nitride (AlN), aluminum hydroxide (Al (OH ₃ ), silicon dioxide (SiO ₂ ), magnesium carbonate (MgCO ₃ ), magnesium hydroxide (Mg (OH) ₂ ), calcium carbonate (CaCO ₃ ), clay, talc, mica, titanium oxide (TiO ₂ ), oxidation Zinc (ZnO), silicon nitride, silicon carbide, boron carbide, titanium carbide , Calcium oxide, zeolite, amorphous aluminosilicate, synthetic silica, alumina, barium sulfate, aluminum sulfate, magnesium hydroxide, barium titanate, ferrite and other inorganic fillers, diamond, graphite, graphite, carbon black, acetylene Examples thereof include carbon-based fillers such as black, ketjen black, furnace black, carbon fiber, carbon nanotube, graphene, and diamond.

  The filler-containing curable resin composition of the present invention includes a soluble polyfunctional vinyl copolymer (A), an initiator (B), a solvent (C), and a filler (D). The use amount (in terms of solid content) of the soluble polyfunctional vinyl copolymer (A) is, for example, 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight with respect to 100 parts by weight of the filler (D), for example. More preferably, it is 2 to 30 parts by weight. If the amount of the soluble polyfunctional vinyl copolymer (A) used is too small, the dispersibility of the filler tends to be lowered, and conversely if too large, aggregates of the filler tend to be generated.

The total solid content concentration in the curable resin composition or the filler-containing curable resin composition can be appropriately selected within a range not impairing the coating workability and the like, for example, 0.1 to 75% by weight, preferably 0.2 to 70% by weight, more preferably 1 to 65% by weight. Moreover, content of the filler (D) in a filler containing curable resin composition is 0.1-74.9 weight%, for example, Preferably it is 1-70 weight%.
The solvent (C) is contained in the composition at 25 to 99% by weight, preferably 30 to 70% by weight. And it is preferable to use this as a coating liquid. Moreover, the usage-amount of the resin component per 100 mass parts of said coating liquids is 0.1-40 mass parts in solid content, and 0.2-20 mass parts is preferable.

In the filler-containing curable resin composition of the present invention, a thickener (E) is blended as a component that increases the dispersibility of the filler (D) in the curable resin composition and suppresses sedimentation of the filler. You can also
The thickener (E) is not particularly limited, but polyvinyl alcohol, polyvinyl acetal, polyacrylic acid, fluorine-containing polymer, cellulose polymer, starch polymer, styrene polymer, acrylic polymer, styrene -Conventionally well-known resin, such as an acrylic ester copolymer, polyamide, a polyimide, and a polyamideimide, is mentioned. These resin components can be obtained from the market and used as they are, but derivatives thereof prepared in consideration of solubility in a solvent are more preferable.
The usage-amount of a thickener (E) is 1-1000 mass parts per 100 mass parts of soluble polyfunctional vinyl copolymers (A), and 5-500 mass parts is preferable.

It does not specifically limit as a preparation method of a filler containing curable resin composition, A filler (D), a soluble polyfunctional vinyl copolymer (A), an initiator (B), and a solvent (C) are mixed. Can be prepared. The order of addition of each component is not particularly limited. For example, the polyfunctional vinyl copolymer (A) and the initiator (B) are added to a slurry solution containing a filler (D) and a solvent (C), and a mixer is used. By using and mixing, a filler-containing curable resin composition can be prepared. For mixing and stirring for producing the filler-containing curable resin composition, it is necessary to select a mixer capable of stirring to such an extent that no filler aggregates remain in the slurry and a sufficient dispersion condition as necessary. There is. The degree of dispersion can be measured by a particle gauge, but it is preferable to mix and disperse so that aggregates larger than at least 100 μm are eliminated. Mixers that meet these conditions include, for example, bead mills, jet mills, roll mills, hammer mills, vibration mills, ball mills, sand mills, pearl mills, spike mills, agitator mills, coball mills, defoamers, pigment dispersers, crushers. And mixers such as a mixer, an ultrasonic disperser, a homogenizer, a planetary mixer, and a Hobart mixer.
The preparation of the filler-containing curable resin composition (mixing operation of each component) is preferably performed at least part of the process under reduced pressure. Thereby, it can prevent that a bubble arises in the filler layer obtained. The degree of pressure reduction is preferably about 5.0 × 10 ^{4 to} 5.0 × 10 ⁵ Pa as an absolute pressure.

  The filler-containing curable resin composition coating film formed using the filler-containing curable resin composition of the present invention is coated on the surface of an appropriate base material such as a metal foil or a resin film. It can manufacture by apply | coating a functional resin composition and then removing and drying a solvent. The coating film thus produced is composed of a soluble polyfunctional vinyl copolymer (A), an initiator (B) and a filler (D) on the substrate, and optional additional components used as necessary. The layer containing is bound. The base material with a coating film having a layer formed from the filler-containing curable resin composition of the present invention on the surface of the base material is excellent in the binding property between the base material and the coating film and is given by the filler. Gives a functional coating with excellent functional properties.

There is no restriction | limiting in particular as a raw material of the said base material, Various plastic materials [For example, α-, such as polyethylene (PE), polypropylene (PP), an ethylene propylene copolymer, an ethylene-vinyl acetate copolymer (EVA), etc.). Olefin resins containing olefin as a monomer component; polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polyvinyl chloride (PVC); vinyl acetate resin; polyphenylene sulfide ( PPS); polyamide resins such as polyamide (nylon), wholly aromatic polyamide (aramid); polyimide resins; polyether ether ketone (PEEK), etc.], rubber materials (for example, natural rubber, synthetic rubber, silicon rubber, etc.) , Metal materials (e.g., Luminium, copper, iron, nickel, stainless steel, etc.), paper materials (eg, paper, paper-like substances, etc.), wood materials (eg, wood, wood boards such as MDF, plywood, etc.), fiber materials (eg, nonwoven fabric, woven) Cloth, etc.), leather materials, inorganic materials (for example, stone, concrete, etc.), glass materials, porcelain materials, and other various materials. Among these, as the base material, plastic material base materials (plastic sheets, films, etc.) and metal materials (metal foil, punching metal, expanded metal, wire mesh, foam metal, mesh metal fiber sintered body, metal plating) Resin plate) is preferable.
The shape and thickness of the base material are not particularly limited, but it is preferable to use a film or sheet having a thickness of about 0.001 to 0.5 mm.

  There is no restriction | limiting in particular about the coating method to the base material of a curable resin composition containing a filler. The coating can be performed by an appropriate method such as a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a dipping method, or a brush coating method. The coating amount of the filler-containing curable resin composition is not particularly limited, but is preferably an amount such that the thickness of the filler layer formed after removing the solvent is 0.001 to 5 mm. It is more preferable to set it as the quantity which will be -2mm.

  The method for removing the solvent from the coated film after coating is not particularly limited, and may be, for example, drying with warm air, hot air or low-humidity air; vacuum drying; drying by irradiation with (far) infrared rays or electron beams. The drying speed may be appropriately set so that the solvent can be removed as quickly as possible within a speed range in which the filler layer does not crack due to stress concentration or the filler layer does not peel from the substrate. it can.

  The cured product of the present invention is obtained by drying and curing the filler-containing curable resin composition coating film of the present invention by a method such as heating. In the heat drying, it is preferable to heat at 60 ° C. or higher for 1 second or longer, more preferably at 60 ° C. or higher and 200 ° C. or lower for 1 second or longer and 60 minutes or shorter. If these conditions are satisfied, the soluble polyfunctional vinyl copolymer (A) in the coating film and the base material of the coating film layer formed by sufficiently crosslinking the polymers such as the resin component to be added as necessary The functional properties of the filler layer for various applications can be improved. If the heat treatment condition is less than 60 ° C. or less than 1 second, the adhesion of the coating layer to the substrate of the coating film layer and the functional properties of the filler layer to the cured coating film may not be satisfied, which is not preferable.

  If necessary, the curable resin composition of the present invention can be mixed with a substrate such as carbon fiber or glass fiber to form a curable composite material. For the curable composite material, a coupling agent or an adhesive can be used for the purpose of improving the adhesiveness at the interface between the resin and the substrate, if necessary. As the coupling agent, general materials such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent, and the like can be used. Examples of the adhesive include, but are not limited to, epoxy, acrylic, phenol, and cyanoacrylate. Lamination molding and curing can be performed under the same conditions as in the production of ordinary cured composite materials.

  According to the present invention, although it is a material suitable for an aqueous slurry, it has an excellent dispersion function with respect to a functional filler, and also exhibits an excellent function as a binder, with a balance of adhesion, heat resistance and flexibility. Excellent functional coating film can be formed, the viscosity is maintained even after long-term storage, the functional filler is less likely to settle and segregate, and the water-based functional filler dispersion coating liquid is highly dispersible. Can be provided. For this reason, it becomes possible to form a highly functional coating film with excellent adhesion, in which the functional filler is uniformly dispersed, so that electronic material paints, inks, toners, rubber / plastics, ceramics, magnetic materials, adhesives It can be expected to be used in various fields such as agents, liquid crystal color filters, electrode materials for storage batteries such as secondary batteries and capacitors.

  The use of the substrate having the cured product of the present invention is not particularly limited, and examples thereof include conductive coatings such as conductive adhesives, conductive paints, and conductive inks. In addition, coating-type magnetic recording media such as audio tapes, video tapes, and floppy disks, or photocatalysts such as a photocatalyst coating and a photocatalyst-coated body are also suitable applications. Power sources for driving electric vehicles, hybrid vehicles, power tools, etc .; batteries for personal computers, mobile phones, etc .; electrodes for storage devices such as storage batteries attached to power generators such as solar power generation and wind power generation, coating agents, separators, sealing Agents are also a suitable use. Furthermore, lenses (for example, glasses and camera lenses), prisms, vehicle members such as automobiles and railway vehicles (window glass, illumination lamp covers, rearview mirrors, etc.), building members (for example, outer wall materials, inner wall materials, window frames) , Window glass, etc.), machine components, traffic signs, various display devices, advertising towers, sound insulation walls (for roads, railways, etc.), bridges, guard rails, tunnels, insulators, solar cell covers, solar water heaters Covers, lighting fixtures, bathroom items, bathroom members (eg, mirrors, bathtubs, etc.), kitchen items, kitchen items (eg, kitchen panels, sinks, range hoods, ventilation fans, etc.), air conditioning, toilet articles, toilet members (eg, toilet bowls) Etc.), antibacterial / antifungal, deodorizing, air purification, water purification, antifouling effects, and films, sheets, seals and the like for application to the surface of the article.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, all the parts in each example are parts by weight, and the physical properties were measured by the following methods.

1) Molecular weight and molecular weight distribution of copolymer (soluble polyfunctional aromatic copolymer) For molecular weight and molecular weight distribution measurement, GPC (manufactured by Tosoh Corporation, HLC-8120GPC) was used, tetrahydrofuran as a solvent, flow rate of 1.0 ml / min. The column temperature was 38 ° C., and a calibration curve using monodisperse polystyrene was used.

2) Copolymer structure Determined by ¹³ C-NMR and ¹ H-NMR analysis using a JNM-LA600 nuclear magnetic resonance spectrometer manufactured by JEOL. Chloroform-d ₁ was used as a solvent, and the tetramethylsilane resonance line was used as an internal standard.
3) Analysis of terminal groups For the terminal groups of the copolymer, the consumption of each monomer during polymerization was measured using a GC-2010 gas chromatograph measuring device manufactured by Shimadzu Corporation, with 4-acetylbiphenyl as an internal standard substance. It was measured. Furthermore, the number average molecular weight was measured using GPC (manufactured by Tosoh Corporation, HLC-8120GPC) using tetrahydrofuran as a solvent, a flow rate of 1.0 ml / min, a column temperature of 38 ° C., and a calibration curve using monodisperse polystyrene. And the content of the structural unit of copolymers, such as a vinyl group and vinylene group, was determined by < ¹³ > C-NMR and < ¹ > H-NMR analysis using JEOL JNM-LA600 type | mold nuclear magnetic resonance spectrometer. Chloroform-d ₁ was used as a solvent, and the tetramethylsilane resonance line was used as an internal standard. And content of ta1 and tb1 was computed from these measurement results.

4) Solvent solubility The evaluation of the solubility of the copolymer was performed by adding 5.0 g of the solvent to 5.0 g of the copolymer and stirring to dissolve the copolymer. This was left still and the presence or absence of insoluble matter, such as a gel, was confirmed visually. As the solvent, methanol, ethanol, isopropanol, THF (tetrahydrofuran), dichloroethane, dichloromethane, and chloroform were used.

Example 1
Acrylic acid 2.85 mol (209.6 g), 2-hydroxy-3-acryloyloxypropyl methacrylate (light ester G201-P manufactured by Kyoeisha Chemical Co., Ltd.) 0.15 mol (32.1 g), 3-mercaptopropionic acid 0. 075 mol (8.0 g) and 117.1 g of 2-propanol were charged into a 1.0 L reactor, and an industrial pure product of 0.1 mmol of bis (4-tert-butylcyclohexyl) peroxydicarbonate at 50 ° C. (Purity 90%; NOF Co., Ltd., Parroyl TCP, hereinafter, TCP) dissolved in 3.0 g of 2-propanol was added to start polymerization. In the first hour, the second hour, and the third hour after the start of polymerization, 0.2 mmol of TCP and 0.075 mol (8.0 g) of 3-mercaptopropionic acid were added, and the reaction was allowed to proceed for 4 hours. After the polymerization solution was stopped with tert-butylcatechol, the produced polymer was precipitated using hexane to remove unreacted monomers. The polymer was purified by repeating redissolving with 2-propanol and washing with hexane. Then, it was devolatilized under reduced pressure at 60 ° C. to remove the remaining hexane, and the polymer was recovered as a 2-propanol solution. 460.0g of copolymer A solution was obtained, and solid content was 34.3 wt%.

Mn of the obtained copolymer A was 13700, Mw was 79100, and Mw / Mn was 5.78. The structural units (a), (b) and (b1) present in the copolymer A are quantified by performing LC analysis, GPC measurement, FT-IR, ¹³ C-NMR and ¹ H-NMR analysis. It was. From the result, the molar fraction of the structural unit (b1) calculated by the formula [(b1)] / [(a) + (b)] was 0.054. The molar fraction of the structural unit (c) calculated by the formula [(c)] / [(a) + (b) + (c)] was 0.025.
Copolymer A was soluble in methanol, ethanol, isopropanol, THF, dichloroethane, dichloromethane, and chloroform at a concentration of 50 wt%, and no gel was observed.

  After adding 150 g of water to the 2-propanol solution of copolymer A, the solution was neutralized so as to have a pH of 6 to 7 by adding 49.3 g of sodium carbonate. 2-Propanol was removed by heating / concentration and additional addition of water to obtain 461.1 g of a partial sodium aqueous solution of copolymer A. The solid content was 43.5 wt%. The aqueous solution of the partial sodium salt of copolymer A was a colorless and transparent aqueous solution, and no gel was observed.

Example 2
Acrylic acid 2.50 mol (183.8 g), methacrylic acid 0.35 mol (30.7 g), 2-hydroxy-3-acryloyloxypropyl methacrylate 0.15 mol (32.1 g), 3-mercaptopropionic acid A solution in which 0.075 mol (8.0 g) and 117.1 g of 2-propanol were charged into a 1.0 L reactor, and 0.1 mmol of TCP was dissolved in 3.0 g of 2-propanol at 50 ° C. The polymerization was started by adding. In the first hour, the second hour, and the third hour after the start of polymerization, 0.2 mmol of TCP and 0.075 mol (8.0 g) of 3-mercaptopropionic acid were added, and the reaction was allowed to proceed for 4 hours. After the polymerization solution was stopped with tert-butylcatechol, the produced polymer was precipitated using hexane to remove unreacted monomers. The polymer was purified by repeating redissolving with 2-propanol and washing with hexane. Then, it was devolatilized under reduced pressure at 60 ° C. to remove the remaining hexane, and the polymer was recovered as a 2-propanol solution. The obtained polymer solution was 493.4 g, and the solid content was 30.3 wt%.

Mn of the obtained copolymer B was 14800, Mw was 86700, and Mw / Mn was 5.86. When the molar fractions of the structural units (b1) and (c) were determined in the same manner as in Example 1, they were 0.051 and 0.023, respectively.
Copolymer B was soluble in methanol, ethanol, isopropanol, THF, dichloroethane, dichloromethane, and chloroform at a concentration of 50 wt%, and no gel was observed.

  After adding 150 g of water to the 2-propanol solution of copolymer B, neutralization was performed by adding 45.8 g of sodium carbonate to a pH of 6-7. 2-Propanol was removed by heating / concentration and additional addition of water to obtain 388.4 g of a partial sodium salt aqueous solution of copolymer B. The solid content was 50.3 wt%. The partial sodium salt aqueous solution of copolymer B was a colorless and transparent aqueous solution, and no gel was observed.

Example 3
2.85 mol (209.6 g) of acrylic acid, 0.15 mol (34.2 g) of glycerol dimethacrylate (produced by Kyoeisha Chemical Co., Ltd.), 0.075 mol (8.0 g) of 3-mercaptopropionic acid, 117.1 g of 2-propanol was put into a 1.0 L reactor, and a solution in which 0.1 mmol of TCP was dissolved in 3.0 g of 2-propanol was added at 50 ° C. to start polymerization. In the first hour, the second hour, and the third hour after the start of polymerization, 0.2 mmol of TCP and 0.075 mol (8.0 g) of 3-mercaptopropionic acid were added, and the reaction was allowed to proceed for 4 hours. After the polymerization solution was stopped with tert-butylcatechol, the produced polymer was precipitated using hexane to remove unreacted monomers. The polymer was purified by repeating redissolving with 2-propanol and washing with hexane. Then, it was devolatilized under reduced pressure at 60 ° C. to remove the remaining hexane, and the polymer was recovered as a 2-propanol solution. The obtained polymer solution was weighed to confirm that 433.4 g of copolymer C solution was obtained. When solid content measurement was performed, solid content was 32.5 wt%.

  Mn of the obtained copolymer C was 11200, Mw was 69200, and Mw / Mn was 6.18. When the molar fractions of the structural units (b1) and (c) were determined in the same manner as in Example 1, they were 0.051 and 0.026, respectively.

  Copolymer C was soluble in methanol, ethanol, isopropanol, THF, dichloroethane, dichloromethane, and chloroform at a concentration of 50 wt%, and no gel was observed.

  After adding 150 g of water to the 2-propanol solution of copolymer C, the solution was neutralized so as to have a pH of 6 to 7 by adding 43.6 g of sodium carbonate. 2-Propanol was removed by heating / concentration and additional addition of water to obtain 395.0 g of a partial sodium salt aqueous solution of copolymer C. The solid content was 46.7 wt%. The partial sodium salt aqueous solution of copolymer C was a colorless and transparent aqueous solution, and no gel was observed.

Example 4
Acrylic acid 2.85 mol (209.6 g), 2-hydroxy-3-acryloyloxypropyl methacrylate 0.15 mol (32.1 g), thioglycolic acid 0.075 mol (6.9 g), 2-propanol 117 0.1 g was put into a 1.0 L reactor, and a solution of 0.1 mmol of TCP dissolved in 3.0 g of 2-propanol was added at 50 ° C. to start polymerization. In the first hour, the second hour, and the third hour after the initiation of polymerization, 0.2 mmol of TCP and 0.075 mol (6.9 g) of thioglycolic acid were added, and the reaction was allowed to proceed for 4 hours. After the polymerization solution was stopped with tert-butylcatechol, the produced polymer was precipitated using hexane to remove unreacted monomers. The polymer was purified by repeating redissolving with 2-propanol and washing with hexane. Then, it was devolatilized under reduced pressure at 60 ° C. to remove the remaining hexane, and the polymer was recovered as a 2-propanol solution. 466.1g of copolymer D solution was obtained, and solid content was 33.6 wt%.

Mn of the obtained copolymer D was 13200, Mw was 75600, and Mw / Mn was 5.73. When the molar fractions of the structural units (b1) and (c) were determined in the same manner as in Example 1, they were 0.055 and 0.028, respectively.
Copolymer D was soluble in methanol, ethanol, isopropanol, THF, dichloroethane, dichloromethane, and chloroform at a concentration of 50 wt%, and no gel formation was observed.

  After adding 150 g of water to the 2-propanol solution of copolymer D, 48.9 g of sodium carbonate was added to neutralize the pH to 6-7. 2-Propanol was removed by heating / concentration and additional addition of water to obtain 497.7 g of a partial sodium salt aqueous solution of copolymer D. The solid content was measured and found to be 41.3 wt%. The partial sodium salt aqueous solution of copolymer D was a colorless and transparent aqueous solution, and the formation of gel was not observed.

Comparative Example 1
Acrylic acid 2.85 mol (209.6 g), 2-hydroxy-3-acryloyloxypropyl methacrylate 0.15 mol (32.1 g), 1-dodecanethiol 0.075 mol (15.2 g), 2-propanol 117.1 g was put into a 1.0 L reactor, and a solution prepared by dissolving 0.1 mmol of TCP in 3.0 g of 2-propanol at 50 ° C. was added to start polymerization. At 1 hour, 2 hours and 3 hours after the start of polymerization, 0.2 mmol of TCP and 0.075 mol (15.2 g) of 1-dodecanethiol were added, and the reaction was allowed to proceed for 5 hours. After the polymerization solution was stopped with tert-butylcatechol, the produced polymer was precipitated using hexane to remove unreacted monomers. The polymer was purified by repeating redissolving with 2-propanol and washing with hexane. Then, it was devolatilized under reduced pressure at 60 ° C. to remove the remaining hexane, and the polymer was recovered as a 2-propanol solution. 462.7g of copolymer E solutions were obtained, and solid content was 31.6 wt%.

Copolymer E had Mn of 14700, Mw of 89300, and Mw / Mn of 6.08. When the molar fractions of the structural units (b1) and (c ′) were determined in the same manner as in Example 1, they were 0.049 and 0.022, respectively. Here, the structural unit (c ′) is a structural unit derived from 1-dodecanethiol.
Copolymer E was soluble in methanol, ethanol, isopropanol, THF, dichloroethane, dichloromethane, and chloroform at a concentration of 50 wt%, and no gel formation was observed.

  After adding 150 g of water to the 2-propanol solution of copolymer E, 45.7 g of sodium carbonate was added to neutralize the pH to 6-7. 2-Propanol was removed by heating, concentrating, and adding water to obtain 482.2 g of a partial sodium aqueous solution of copolymer E. The solid content was 39.8 wt%. The partial sodium aqueous solution of copolymer E was a colorless and transparent aqueous solution, and the formation of gel was not observed.

Comparative Example 2
2.85 mol (209.6 g) of acrylic acid, 0.15 mol (36.3 g) of diethylene glycol dimethacrylate (Light Ester 2EG manufactured by Kyoeisha Chemical), 0.075 mol (8.0 g) of 3-mercaptopropionic acid, 117.1 g of 2-propanol was put into a 1.0 L reactor, and a solution in which 0.1 mmol of TCP was dissolved in 3.0 g of 2-propanol was added at 50 ° C. to start polymerization. In the first hour, the second hour, and the third hour after the start of polymerization, 0.2 mmol of TCP and 0.075 mol (8.0 g) of 3-mercaptopropionic acid were added, and the reaction was allowed to proceed for 5 hours. After the polymerization solution was stopped with tert-butylcatechol, the produced polymer was precipitated using hexane to remove unreacted monomers. The polymer was purified by repeating redissolving with 2-propanol and washing with hexane. Then, it was devolatilized under reduced pressure at 60 ° C. to remove the remaining hexane, and the polymer was recovered as a 2-propanol solution. 414.2 g of copolymer F solution was obtained, and the solid content was 35.3 wt%.

Mn of the obtained copolymer F was 15100, Mw was 91800, and Mw / Mn was 6.08. When the molar fractions of the structural units (b1 ′) and (c) were determined in the same manner as in Example 1, they were 0.048 and 0.024, respectively. Here, the structural unit (b1 ′) is a structural unit derived from diethylene glycol dimethacrylate and having a methacrylate group.
Copolymer F was soluble in methanol, ethanol, isopropanol, THF, dichloroethane, dichloromethane, and chloroform at a concentration of 50 wt%, and no gel formation was observed.

  After adding 150 g of water to the 2-propanol solution of copolymer F, 50.2 g of sodium carbonate was added to neutralize the pH to 6-7. 2-Propanol was removed by heating / concentration and addition of water to obtain 564.8 g of a partial sodium aqueous solution of copolymer F. The solid content was 37.8 wt%. The partial sodium aqueous solution of copolymer F was a colorless and transparent aqueous solution, and no gel was observed.

Example 5
As the binder resin, the partial sodium salt of copolymer A obtained in Example 1 was used, and 4,4′-azobis (4-cyanovaleric acid) (trade name; V-501) as a polymerization initiator was used therefor. Manufactured by Wako Pure Chemical Industries, Ltd.), AO-60 as an antioxidant, ion-exchanged water as a solvent, and carbon as a filler, and kneaded in a batch kneader for 30 minutes to prepare a water-based conductive paint. Here, 4 parts of copolymer-A partial sodium salt, 1 part of thickener (trade name; CMC1120, manufactured by Daicel Corporation) and 60 parts of carbon with respect to 100 parts of the obtained water-based conductive paint. Each part was used. At this time, the ion exchange water was added so that the carbon had a solid content concentration shown in Table 1 below.
As the carbon, 20 parts of carbon black was used with respect to 80 parts of graphite.

Examples 6-8, Comparative Examples 3-4
A water-based conductive paint was obtained in the same manner as in Example 5 except that the formulation shown in Table 1 was used.

Table 1 shows the results of evaluating the fluidity, paint properties, film strength, resistance value, acid resistance and heat resistance of the obtained water-based conductive paint. The same items as in Example 5 were tested and evaluated. The results obtained by these tests are shown in Table 1.
In Table 1, in the kind of binder resin, A to F means partial sodium salts of the copolymers A to F. For example, A means a partial sodium salt of copolymer A.
In addition, the following method evaluated the characteristic of the coating material and its hardened | cured material.

5) Flowability: Appearance of sheet coated and dried with water-based conductive paint Appearance of conductive paint sheet surface formed by drying and curing a coating film formed with a doctor blade with a gap of 500 μm on PET film for 1 hour at 120 ° C. The presence of cracks or the like was judged. In Table 1, when there was no defect such as a crack, it was indicated as ◯, and when there was a defect such as a crack, it was indicated as x.

6) Paint property: sheet smoothness The roughness of the conductive paint sheet surface was measured with a laser depth meter. Ra was determined according to JIS B0633: '01. Ra has shown that it is smooth as it is 10 micrometers or less.

7) Film strength: peel strength A coating film formed by applying a water-based conductive paint to a SUS plate with a doctor blade with a gap of 500 μm is dried at 90 ° C. for 1 hour, and then an adhesive tape with a width of 10 mm is pasted thereon and peeled 180 ° The strength was measured. It shows that the peel strength is good when it is 10 N or more.

8) Resistance value A coating film formed by applying a water-based conductive paint on a PET film with a doctor blade with a gap of 500 μm is dried at 120 ° C. for 1 hour, cut into a predetermined size, and a metal terminal is brought into contact with the surface. The volume resistivity was measured. It shows that the volume resistivity is good when it is 500 mΩcm or less.

9) Acid resistance: resistance value The SUS plate coated with the conductive paint obtained by the above film strength evaluation and dried was immersed in acid water adjusted to pH 3 with sulfuric acid, heated to 60 ° C., and immersed for 100 hours. Thereafter, the resistance value (volume resistivity) of the sheet washed with ion-exchanged water and dried was measured. It shows that the volume resistivity is good when it is 500 mΩcm or less.

10) Heat resistance: resistance value The SUS plate coated with the conductive paint obtained by the above film strength evaluation and dried is placed in an air oven at 130 ° C., left for 120 hours, washed with ion-exchanged water, and dried. Similarly, the resistance value (volume resistivity) was measured. It shows that the volume resistivity is good when it is 500 mΩcm or less.

Example 9
Acrylic acid 3.20 mol (235.3 g), 2-hydroxy-3-acryloyloxypropyl methacrylate (light ester G201-P manufactured by Kyoeisha Chemical Co., Ltd.) 0.8 mol (171.4 g), 3-mercaptopropionic acid 40 mol (42.5 g) and 218.6 g of 2-propanol were put into a 1.0 L reactor, and 2.0 mmol of industrial pure product of bis (4-t-butylcyclohexyl) peroxydicarbonate at 50 ° C. (Purity 90%; NOF Co., Ltd., Parroyl TCP, hereinafter, TCP) dissolved in 3.0 g of 2-propanol was added to start polymerization. After the start of polymerization, at 1 hour, 2 hours, 3 hours, and 4 hours, 2.0 mmol of TCP was additionally added, and polymerization was carried out for 5 hours. After stopping the polymerization reaction with tert-butylcatechol, the produced polymer was precipitated using hexane to remove unreacted monomers. The polymer was purified by repeating redissolving with 2-propanol and washing with hexane. Then, it was devolatilized under reduced pressure at 60 ° C. to remove the remaining hexane, and the polymer was recovered as a 2-propanol solution. 660.6g of 2-propanol solutions of copolymer G were obtained, and solid content was 40.2 wt%.

Mn of the obtained copolymer G was 23100, Mw was 143000, and Mw / Mn was 6.19. The structural units (a), (b) and (b1) present in the copolymer G are quantified by performing LC analysis, GPC measurement, FT-IR, ¹³ C-NMR and ¹ H-NMR analysis. It was. From the result, the molar fraction of the structural unit (b1) calculated by the formula [(b1)] / [(a) + (b)] was 0.16. Further, the molar fraction of the structural unit (c) calculated by the formula [(c)] / [(a) + (b) + (c)] was 0.028.
Copolymer G was soluble in methanol, ethanol, isopropanol, THF, dichloroethane, dichloromethane, and chloroform at a concentration of 50 wt%, and no gel formation was observed.

Example 10
(Preparation of iron oxide / titanium oxide composite oxide fine particle sol)
0.4 g of ferric chloride in terms of Fe ₂ O ₃ and 99.6 g of titanium tetrachloride in terms of TiO ₂ were dissolved in pure water to prepare a 10 kg mixed aqueous solution. To this mixed aqueous solution, a 28% ammonia aqueous solution at 4 ° C. was rapidly added while cooling so that the liquid temperature did not exceed 10 ° C., and the addition was terminated when the pH reached 7.5. The temperature of the coprecipitation gel of hydrated iron oxide and hydrated titanium oxide produced at this time was 9.8 ° C.

After dehydrating and washing the obtained coprecipitated gel, 910 g of hydrogen peroxide solution with a H ₂ O ₂ concentration of 35 wt% and 200 g of pure water were added to 880 g of the coprecipitated gel, and heated at 80 ° C. for 3 hours to An orange solution (liquid M) (1990 g) was obtained.

  3005 g of water was added to 995 g of this liquid M, and heat treatment was carried out at 200 ° C. for 20 hours in an autoclave to obtain a sol in which iron oxide / titanium oxide composite oxide fine particles were dispersed.

  After 4000 ml of methanol was added to this sol, 2 g of methyltrimethoxysilane was added and aged at 50 ° C. for 1 hour, and then water was removed by solvent substitution to obtain a solid oxide concentration of 20% by weight of iron oxide / titanium oxide composite oxide. 200 g of fine particle-dispersed methanol sol was obtained. The average particle diameter of the composite oxide fine particles was 8 nm as measured by transmission electron micrograph.

(Preparation of coating solution for forming transparent film)
50 g of methanol sol in which the fine particles of the iron oxide / titanium oxide composite oxide are dispersed, 2.5 g of a 2-propanol solution of the copolymer G, and 4,4′-azobis (4-cyanovaleric acid) (trade name; V-501 (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed to prepare a coating solution for forming a transparent film.

(Preparation of substrate with transparent coating)
The said coating liquid was apply | coated with the spin coater on the glass base material (50 mm x 50 mm), and it pre-dried at 50 degreeC, and formed the photocatalyst coating film. Furthermore, after drying at 70 degreeC, it heat-hardened at 120 degreeC and produced the base material with a transparent film. The thickness of the coating was 1 μm, and the hardness of the coating was 5H in pencil hardness.

(Measurement of photocatalytic activity)
Place the above coated substrate in a quartz container (length 150 mm x width 150 mm x height 60 mm), replace with nitrogen gas, seal, and then inject acetaldehyde to a concentration of 50 ppm. A black light (ultraviolet wavelength: 365 nm, intensity: 0.6 mW / cm ² ) was irradiated for 1 hour from a height of 100 mm. Subsequently, the concentration of acetaldehyde remaining in the container was measured by gas chromatography, and the photocatalytic activity was evaluated based on the reduction rate of acetaldehyde. As a result, the photocatalytic activity was 81%.

Claims (15)

A structural unit (a) derived from (meth) acrylic acid, a structural unit (b) derived from a bifunctional (meth) acrylate compound having a hydroxyl group represented by the following formula (2),

(Wherein, R ² and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ³ and R ⁴ each independently represent an alkylene group having 1 to 10 carbon atoms.)
And a copolymer having a structural unit (c) derived from a thiol compound having a carboxyl group,
At least a part of the structural unit (b) is a structural unit (b1) containing a reactive (meth) acrylate group present in the copolymer chain, and the molar fraction of the structural unit (b1) is represented by the following formula: Satisfying (3), having the structural unit (c) at the terminal, and the molar fraction of the structural unit (c) satisfying the following formula (4);
(B1) / [(a) + (b)] ≧ 0.005 (3)
0.001 ≦ (c) / [(a) + (b) + (c)] ≦ 0.5 (4)
(In the formulas (3) and (4), (a), (b), (c) and (b1) are the abundances of the structural units (a), (b), (c) and (b1) ( Mol).)
And a hydroxyl group characterized in that the copolymer has a number average molecular weight Mn of 1000 to 2,000,000, a molecular weight distribution of 500.0 or less, and is soluble in methanol, ethanol, isopropanol or tetrahydrofuran A soluble polyfunctional vinyl copolymer having a carboxyl group. (Meth) acrylic acid, a bifunctional (meth) acrylate compound having a hydroxyl group represented by the following formula (2),

(Wherein, R ² and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ³ and R ⁴ each independently represent an alkylene group having 1 to 10 carbon atoms.)
And a monomer containing a carboxyl group-containing thiol compound is copolymerized. The method for producing a soluble polyfunctional vinyl copolymer according to claim 1.   A water-soluble polyfunctional vinyl copolymer, wherein at least part of the COOH groups of the soluble polyfunctional vinyl copolymer according to claim 1 is COOM (M is an alkali metal or ammonium).   The method for producing a water-soluble polyfunctional vinyl copolymer according to claim 3, wherein the soluble polyfunctional vinyl copolymer according to claim 1 is neutralized with an alkali.   A curable resin composition comprising the soluble polyfunctional vinyl copolymer (A) according to claim 1, an initiator (B), and a solvent (C).   The curable resin composition according to claim 5, which is a filler-containing curable resin composition containing a filler (D).   The curable resin composition of Claim 6 containing a thickener (E).   A curable resin composition comprising the water-soluble polyfunctional vinyl copolymer (A1) according to claim 3, an initiator (B), and an aqueous solvent (C1).   It is a filler containing curable resin composition containing a filler (D) or a filler (D) and a thickener (E), The curable resin composition of Claim 8 characterized by the above-mentioned.   The coating film which consists of a curable resin composition in any one of Claims 5-7.   A coating film comprising the curable resin composition according to claim 8 or 9.   Hardened | cured material of the curable resin composition in any one of Claims 5-7.   A cured product of the curable resin composition according to claim 8.   A cured product of the coating film according to claim 10. A cured product of the coating film according to claim 11.