JP2019044091A - Curable resin composition, and coating film and cured product thereof - Google Patents

Abstract

To provide a novel curable resin composition improved in heat resistance, adhesiveness, compatibility, gas barrier properties, dispersibility and flexibility, and a coating liquid using the same and capable of using an aqueous solvent.SOLUTION: The curable resin composition contains one or more acrylate compounds having a polyether structure, a divinyl aromatic compound, and a monovinyl aromatic compound or contains a prepolymer derived by reacting them. The curable resin composition can be used without a solvent or with an aqueous solvent or an alcoholic solvent.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition having improved heat resistance, adhesiveness, compatibility, gas barrier properties, dispersibility, and flexibility, and a uniformly dispersed filler. Furthermore, a filler-dispersed curable resin composition comprising a low-odor solvent or an aqueous solvent that enables formation of a conductive coating film with a low environmental load, a coating film thereof, and a cured product thereof, and their Concerning usage technology.

  In recent years, a dispersion liquid or paste containing various functional materials such as conductive fillers, magnetic particles, or photocatalysts (hereinafter also referred to as slurry) is used as a coating liquid, and the coating liquid is applied. Attempts to utilize the functionality of the coated film have been studied in various fields.

  For example, a paste-like conductive coating liquid composed of a conductive filler, binder resin, curing agent, solvent, etc. is used as a conductive adhesive, conductive paint, conductive ink, secondary battery electrode material, etc. (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 biologically-derived dispersion medium that exhibits film-forming ability and dispersibility that can replace conventional petroleum-derived raw materials.

  Here, as a general countermeasure for poor dispersion, addition of a dispersing agent, filler surface treatment, microencapsulation, ultrasonic treatment, introduction of a polar group into a binder resin, 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 a metal oxide fine particle filler with a hydrophilic silane coupling agent (Patent Document 6) have been proposed. Other proposals include applying ultrasonic vibration to paste containing inorganic oxide filler to disperse the filler, or forming an insulating resin on the surface of the conductive filler to form a microcapsule type conductive filler. is there.

  However, organic solvents are mainly used for the 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. 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. Obtained by dispersing and dissolving to prepare a paste-like coating liquid, using a current collector made of a metal foil such as aluminum as a base, and applying the coating liquid on the surface of the base to form a coating film layer A positive electrode plate is disclosed. As the binder resin, a polymer binder containing styrene butadiene rubber and potassium polyacrylate (Patent Document 7), and a resin mainly containing ethylene tetrafluoride (Patent Document 8) are known.

  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 positive electrode plate and the negative electrode plate of the battery. However, the binder resins disclosed in Patent Documents 7 and 8 have problems in flexibility and heat resistance when used 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

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. Providing a binder resin composition capable of forming a functional coating film having an excellent balance of adhesion, heat resistance and flexibility, and providing an aqueous functional filler-dispersed coating liquid There is. More specifically, the present invention provides a low-odor solvent or water-based functional filler-dispersed coating liquid that maintains viscosity even when stored for a long period of time, hardly causes sedimentation and separation of the functional filler, and has high dispersibility. There is. 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. -Conductive adhesives, conductive paints, conductive inks, secondary battery electrode materials, high-performance dielectrics in various fields such as plastics, ceramics, magnetic materials, adhesives, liquid crystal color filters, batteries, etc. It can be expected to be used as a highly functional magnetic material and a functional display material. An object of the present invention is to provide a binder resin composition that can be used in a solvent-free, water-based solvent or alcohol-based solvent in many industrial fields that can contribute to environmental protection and health damage prevention, which are social problems. There is.
From this point of view, the present invention improves the heat resistance, adhesiveness, compatibility, gas barrier properties, dispersibility and flexibility, and is a curable resin composition in which the filler is uniformly dispersed, and has a low environmental impact and conductivity. An object of the present invention is to provide a curable resin composition comprising a low-odor solvent or an aqueous solvent that enables the formation of a coating film, a coating film thereof, a cured product thereof, and a technique for using them.

  As a result of intensive studies, the present inventors have found that an acrylate compound having a polyether structure or a curable resin composition containing a prepolymer derived therefrom solves the above-mentioned problems, and the present invention. Was completed.

（式中、Ｒ¹およびＲ²は水素、炭素数１〜４の直鎖もしくは分岐のアルキル基、またはハロゲンであり、Ｒ³は水素であり、Ｒ⁴は水素または炭素数１〜４のアルキル基であり、ｍは３〜２０の整数である。）

（式中、Ｒ⁵は水素、炭素数１〜４の直鎖もしくは分岐のアルキル基、またはハロゲンであり、Ｒ⁶は炭素数１〜２０の直鎖、分岐もしくは環状のアルキル基、または炭素数６〜３０のアリール基であり、Ｒ⁷は水素であり、およびＲ⁸は水素または炭素数１〜４のアルキル基である。ｎは３〜５０の整数である。）

（式中、Ｒ¹⁰は水素であり、Ｒ¹¹は水素または炭素数１〜４のアルキル基であり、Ｙは水素、炭素数１〜４のアルキル基、炭素数７〜１１のアラルキル基、アリール基、アクリロイル基又はメタクリロイル基であり、かつ、Ｙの内１つ以上がアクリロイル基又はメタクリロイル基であり、ｐは１〜５０の整数であるが、ｐの１つ以上は３＜ｐ≦５０を満足する。Zは活性水素化合物残基を示し、ｑは１〜６の整数である。）
（Ｂ）成分が、ジビニル芳香族化合物であり、
（Ｃ）成分が、モノビニル芳香族化合物であり、
（Ｄ）成分が、充填剤であり、
（Ｆ）成分が、上記（Ａ）成分、（Ｂ）成分及び（Ｃ）成分から誘導されるプレポリマーである。
そして、（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び（Ｆ）成分の総和を１００重量部としたときに、（Ａ）成分が５０〜９９．９重量部、（Ｂ）成分が０．０５〜２５重量部、（Ｃ）成分が０．０５〜２５重量部、（Ｄ）成分が２０〜２０，０００重量部であることを満足する。但し、（Ｆ）成分を含む場合は、（Ｆ）成分を構成する単位中の（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分に由来する単位をそれぞれ（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分として計算する。（Ｆ）成分を構成する単位中にその他の成分を含む場合は、その他の成分は計算から除外される。 The present invention is a curable resin composition containing the components shown in the following (1), (2) or (3), and is used without a solvent or used with an aqueous solvent or an alcohol solvent. It is a curable resin composition characterized by this.
(1) One or more components selected from the following (A) component, (B) component, (C) component, and (D) component (2) The following (A) component, (B) component, and (C) component And the following (F) component and (D) component, or (3) the following (F) component and (D) component,
Here, the component (A) is a diacrylate compound (a1) having a polyether structure represented by the following formula (I), or a diacrylate compound (a1) and the following formula (II) or the following formula (III). An acrylate compound having a polyether structure represented by (a2),

Wherein R ¹ and R ² are hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, or halogen, R ³ is hydrogen, and R ⁴ is hydrogen or alkyl having 1 to 4 carbon atoms. And m is an integer of 3 to 20.)

(Wherein R ⁵ is hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, or halogen, and R ⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms. An aryl group of 6 to 30, R ⁷ is hydrogen, and R ⁸ is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 3 to 50.)

Wherein R ¹⁰ is hydrogen, R ¹¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, Y is hydrogen, an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, aryl A group, an acryloyl group or a methacryloyl group, and at least one of Y is an acryloyl group or a methacryloyl group, and p is an integer of 1 to 50, but at least one of p satisfies 3 <p ≦ 50. Z is an active hydrogen compound residue, and q is an integer of 1 to 6.)
(B) component is a divinyl aromatic compound,
(C) component is a monovinyl aromatic compound,
(D) component is a filler,
The component (F) is a prepolymer derived from the components (A), (B) and (C).
And when the sum total of (A) component, (B) component, (C) component, and (F) component is 100 weight part, (A) component is 50-99.9 weight part, (B) component is 0.05 to 25 parts by weight, (C) component is 0.05 to 25 parts by weight, and (D) component is 20 to 20,000 parts by weight. However, when the component (F) is included, the units derived from the component (A), the component (B), and the component (C) in the units constituting the component (F) are respectively the components (A) and (B). It calculates as a component and (C) component. (F) When other components are included in the unit constituting the component, the other components are excluded from the calculation.

The curable resin composition of the present invention has an embodiment shown in (1), (2) or (3), and any of them may be used.
(1); an embodiment comprising (A) component, (B) component, (C) component, and (D) component,
(2); an embodiment comprising (F) component and (D) component,
(3): The aspect containing 1 or more types of components chosen from (A) component, (B) component, and (C) component, (F) component, and (D) component.

  The curable resin composition of this invention can contain a polymerization initiator as (E) component.

Moreover, this invention is a coating liquid characterized by melt | dissolving said curable resin composition with an aqueous solvent or an alcohol solvent.
This coating liquid may contain a thickener as the component (H).

  Moreover, this invention is a coating film which consists of said curable resin composition. Furthermore, this invention is a hardened | cured material of said curable resin composition.

The curable resin composition of the present invention is a low-odor solvent having a low environmental load, or a material suitable for an aqueous slurry or an intermediate thereof, and has an excellent dispersion function for a functional filler, and a binder. In addition, it exhibits an excellent function, and enables the formation of a functional coating film having an excellent balance of adhesion, heat resistance and flexibility. In addition, the viscosity is maintained even when stored for a long period of time, and the functional filler is less likely to settle 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 In various fields such as liquid crystal color filters, batteries, etc., conductive adhesives, conductive paints, conductive inks, secondary battery electrode materials, high-performance dielectrics, high-performance magnetic materials, functional display materials, etc. It can be expected to be used as
In addition to the properties such as heat resistance, adhesiveness, compatibility, dispersibility and flexibility, the coating film produced from the curable resin composition of the present invention or a cured product thereof has improved ion conductivity and heat deterioration resistance. . For this reason, by using the curable resin composition of the present invention as a binder material for electrode materials for secondary batteries, it is possible to form a functional coating film that contributes to high performance of battery characteristics and improvement of life. To.

The curable resin composition of the present invention includes the above component (A), component (B), component (C), and component (D), component (F), component (D), or One or more components selected from the component (A), the component (B), and the component (C), the component (F), and the component (D) are included.
Since the component (A), the component (B), and the component (C) are polymerizable compounds, they function as monomers. The component (F) is a prepolymer obtained by partially polymerizing the component (A), the component (B), and the component (C), but is a polymerizable component because it remains polymerizable.

  As the component (A), the diacrylate compound (a1) having a polyether structure represented by the above formula (I) is essential, and both the diacrylate compound (a1) are represented by the above formula (II) or the following formula (III). An acrylate compound (a2) having a polyether structure represented by The acrylate compound (a2) may be the acrylate compound (a22) represented by the formula (II), the acrylate compound (a23) represented by the formula (III), or both.

In the general formula (I), R ¹ and R ² are selected from hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, and halogen. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl, and specific examples of the halogen include chlorine, bromine, fluorine and the like. R ¹ and R ² are preferably hydrogen or a methyl group. R ³ is hydrogen and R ⁴ is hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. m is an integer of 3-20. When m is 1 or 2, the curable resin composition exhibits swelling or solubility in the electrolytic solution. m is preferably an integer of 3 to 15, more preferably 3 to 10.

  Specific examples of the diacrylate compound (a1) represented by the general formula (I) include triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, heptaethylene glycol dimethacrylate, Octaethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, hexapropylene glycol dimethacrylate, heptapropylene glycol dimethacrylate, octapropylene glycol dimethacrylate; some of these methacrylates are acrylated Compound replaced by triethylene glycol diaquo Rate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, hexaethylene glycol diacrylate, heptaethylene glycol diacrylate, octaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, Examples include hexapropylene glycol diacrylate, heptapropylene glycol diacrylate, and octapropylene glycol diacrylate.

In the above formula (II), R ⁵ is the same as R ¹ and R ² in formula (I). R ⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms, R ⁷ is hydrogen, and R ⁸ is the same as R ⁴ in formula (I). It is. n is an integer of 3-50.

  Specific examples of the acrylate compound (a22) represented by the general formula (II) include methoxy polyethylene glycol methacrylate, ethoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate, ethoxy polyethylene glycol acrylate, methoxy diethylene glycol methacrylate, ethoxy diethylene glycol acrylate, and methoxy dipropylene. Glycol methacrylate, methoxydipropylene glycol acrylate, methoxyethyl methacrylate, methoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-ethoxyethyl acrylate, butoxyethyl methacrylate, butoxyethyl acrylate, phenoxyethyl methacrylate and phenoxyethyl acrylic Such as over doors and the like.

In the above formula (III), R ¹⁰ is hydrogen, and R ¹¹ is the same as R ⁴ in formula (I). Y is hydrogen, an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, an aryl group, an acryloyl group or a methacryloyl group, and at least one of Y is an acryloyl group or a methacryloyl group, p is an integer of 1 to 50, but one or more of p satisfy 3 <p ≦ 50. q is an integer of 1-6.
Z represents a 3-6 functional active hydrogen compound residue. Examples of the active hydrogen compound used as a starting material for the structural unit of Z include polyhydric alcohol compounds containing 3 to 6 hydroxyl groups in one molecule, such as glycerin, trimethylolpropane, pentaerythritol, ditrimethylol. Examples thereof include aliphatic polyhydric alcohols such as propane and dipentaerythritol; sugar derivatives such as hydrogenated sugar alcohols and glycoside compounds. Of these, glycerin, pentaerythritol, trimethylolpropane, ditrimethylolpropane, dipentaerythritol and the like are preferable.

  As specific examples of the acrylate compound (a23) represented by the general formula (III), an active hydrogen compound such as diglycerin or pentaerythritol is used as a starting material, and a monomer such as ethylene oxide or propylene oxide is added thereto. Furthermore, there are those obtained by esterifying an unsaturated organic acid such as acrylic acid or methacrylic acid, or by dehydrochlorinating an acid chloride such as acrylic acid chloride or methacrylic acid chloride.

The diacrylate compound (a1) having a polyether structure represented by the above formula (I) used as an essential component of the component (A) is chemically stable and heat resistant by forming a crosslinked structure. In addition to having two reactive double bonds that improve adhesion, it has a polyether structure that improves adhesion, compatibility, dispersibility, and flexibility.
The acrylate compound (a2) having a polyether structure represented by the above formula (II) or (III) has at least one reactive double bond, and at the same time has adhesiveness, compatibility, dispersibility, and flexibility. Since the polyether structure is improved, the function of the diacrylate compound (a1) having a polyether structure can be improved or adjusted.

  As the component (B), a divinyl aromatic compound is used. The component (B) increases the dispersibility of the conductive filler and increases the adhesion, flexibility and ionic conductivity of the component (A) by forming a rigid and small cross-linked structure.

  Examples of the divinyl aromatic compound include, but are not limited to, aromatic compounds having two vinyl groups, but include divinylbenzene (including each positional isomer or a mixture thereof), divinylnaphthalene (each positional isomer, or these isomers). Divinyl biphenyl (including each positional isomer or a mixture thereof) is preferably used. Moreover, these can be used individually or in combination of 2 or more types. From the viewpoint of moldability, divinylbenzene (m-isomer, p-isomer, or a mixture of these positional isomers) is more preferable. Here, in the divinyl aromatic compound and the monovinyl aromatic compound, the vinyl group is preferably bonded directly to carbon of the aromatic ring from the viewpoint of reactivity.

  As the component (C), a monovinyl aromatic compound is used. Component (C) increases the dispersibility of the conductive filler.

  Examples of monovinyl aromatic compounds are not limited as long as they are aromatic compounds having one vinyl group, but vinyl aromatic compounds such as styrene, vinyl naphthalene, and vinyl biphenyl; o-methylstyrene, m-methylstyrene, p -Nuclear alkyl substituted vinyl aromatic compounds such as methylstyrene, o, p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene; Preferably, styrene, ethyl vinyl benzene (at each position) because the effect of improving the solvent resistance of the cured product of the coating film of the curable resin composition, the effect of dispersing the filler is high, the cost is low, and the availability is easy. Isomers or mixtures thereof), ethyl vinyl biphenyl (including each positional isomer or mixture thereof), and ethyl vinyl naphthalene (including each positional isomer or mixture thereof). More preferred is styrene or ethylvinylbenzene (m-form, p-form or a mixture of these positional isomers) from the viewpoint of the effect of dispersing the filler and cost.

  In the curable resin composition of the present invention, the component (A), the component (B), and the component (C) can be partially polymerized in advance and contained as a prepolymer (F). When the pre-polymer which is the component (F) is generated, the curing shrinkage rate can be reduced. Particularly, when an aqueous solvent and an alcohol solvent that have a large effect in a solvent-free system but are difficult to dry are used. However, it is preferable because the properties of the coating film after finishing the curing reaction are improved and the reliability of the member is improved.

(F) As a manufacturing method of the prepolymer as a component, the method (1) of heating only the mixture of (A), (B) and (C) component, and adding a small amount of organic peroxide etc. to the said mixture There are a heating method (2), a method (3) in which a small amount of a photopolymerization initiator is added to the mixture and irradiation with ultraviolet rays, and the like. From the viewpoint of controlling the reaction rate, the method (1) is preferable. The reaction temperature is preferably 5 ° C. to 120 ° C. from the viewpoint of controlling the reaction rate. More preferably, it is 40 to 100 ° C, and particularly preferably 50 to 80 ° C.
Moreover, this polymerization reaction can be carried out by bulk polymerization without using a solvent, but can also be carried out in one or more organic solvents that dissolve the prepolymer. As an organic solvent, a compound that does not essentially inhibit radical polymerization and can dissolve a chain transfer agent, an initiator, a monomer component, and a prepolymer to form a uniform solution, and can be used without any particular limitation. Can do.

  Organic solvents that can be used for prepolymer synthesis include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol; acetone, 2-butanone, methyl ethyl ketone, diethyl ketone, methyl Ketones such as propyl ketone, methyl 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; Aromatic hydrocarbons such as benzene, toluene, 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 prepolymer as the component (F) is preferably dissolved in a solvent and has polymerizability. For this purpose, it is preferable to leave some of the two vinyl groups of the component (B) as vinyl groups without reacting them. When a monomer containing a divinyl aromatic compound is polymerized, a crosslink develops to form a cured resin that does not exhibit thermoplasticity or solvent solubility. However, if the reaction is controlled using a chain transfer agent or the like, it is solvent-soluble and polymerizable. Can be obtained. Such a polymerization reaction is known, and such a polymerization method can be employed. The prepolymer of the component (F) may be obtained by polymerizing a monomer containing other monomer components in addition to the components (A), (B), and (C) as long as the effects of the present invention are not impaired. Good.

  In the curable resin composition of the present invention, the contents of the components (A), (B), (C) and (D) are the components (A), (B), and (C) and (F). When the total of the components is 100 parts by weight, the component (A) is 50 to 99.9 parts by weight, the component (B) is 0.05 to 25 parts by weight, and the component (C) is 0.05 to 25 parts by weight. , (D) component is 20 to 20,000 parts by weight.

  In the present specification, for the component (F), the structural units derived from the component (A), the component (B), and the component (C) in the unit constituting the component (F) are respectively represented by the component (A), ( Calculate as B) component and (C) component. That is, it contains f parts by weight of the component (F), the structural unit derived from the component (A) in the component (F) is a%, the structural unit derived from the component (B) and the component (C) is b % And c%, it is calculated that the component (F) includes the component (A) fxa / 100, the component (B) fxb / 100, and the component (C) fxc / 100 (parts by weight). To do. In addition, when referring to the component (A), the component (B), or the component (C), in the calculation of the amount, unless there is a clear contradiction, the component (A) in the component (F), (B) The structural unit derived from the component or the component (C) is calculated as these components. When (A) component, (B) component, (C) component or (F) component contains volatile components, such as a solvent, the quantity is converted into solid content.

When the sum total of (A) component, (B) component, (C) component, and (F) component is 100 weight part, each preferable content is as follows. Note that the component (F) is calculated by converting into the component (A), the component (B), and the component (C) as described above.
The component (A) is 60 to 99.5% by weight, more preferably 70 to 99.0% by weight, and the divinyl aromatic compound as the component (B) is 0.25 to 20% by weight, more preferably 0. The monovinyl aromatic compound as the component (C) is 0.25 to 20% by weight, more preferably 0.5 to 15% by weight.

  The component (A) may contain the diacrylate compound (a1) and the acrylate compound (a2), but the proportion of the diacrylate compound (a1) in the component (A) is 10 to 100 wt%, preferably 20 to 90 wt%. More preferably, it is 25 to 75 wt%. The proportion of the acrylate compound (a2) is calculated from the above.

From another viewpoint, the content of the acrylate compound (a1) represented by the formula (I) is preferably 0.2 to 90% by weight based on the total weight of the components (A) to (C) and (F). Is 0.5 to 80% by weight, more preferably 1.0 to 60% by weight.
The content of the acrylate compound (a22) represented by the formula (II) is 0.2 to 90% by weight, preferably 0.5 to 80% by weight, more preferably 1.0%, based on the total weight. It is good that it is -60 wt%.
The content of the acrylate compound (a23) represented by the general formula (III) is 0.2 to 70% by weight, preferably 0.5 to 60% by weight, more preferably 1.0 to 50% by weight.

Since the curable resin composition of the present invention is useful as a slurry coating solution containing various functional materials, it contains a filler as the component (D).
As the filler, those widely used as various functional materials such as conductive fillers, magnetic particles, and photocatalysts can be widely used. For example, silver, copper, aluminum, iron, stainless steel, nickel, gold, zinc, nickel, tin, lead, chromium, platinum, palladium, tungsten, molybdenum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, Metal fillers such as antimony and 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 ), zinc oxide (ZnO), nitriding Silicon, 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 black, kettle Examples thereof include carbon fillers such as chain black, furnace black, carbon fiber, carbon nanotube, graphene, and diamond.

  The blending amount of the component (D) is appropriately selected depending on the application. For example, for 100 parts by weight of the total amount of the component (A), the component (B), the component (C) and the component (F), for example, It is 20 to 20,000 parts by weight, preferably 40 to 10,000 parts by weight, and more preferably 20 to 5,000 parts by weight. When the component (D) is too much, aggregates of the filler are likely to be generated, and when it is small, the dispersibility of the filler is likely to be lowered.

  The curable resin composition of the present invention can further contain an initiator as the component (E). As will be described later, the resin composition of the present invention is cured by causing a crosslinking reaction by means of heating or the like. At that time, in order to set the reaction temperature low or to promote the crosslinking reaction of unsaturated groups (E) The combination of ingredients is effective. The amount of component (E) is 0.01 to 10% by weight, preferably 0.1 to 8% by weight, based on components (A) to (C) and (F). This initiator is also a radical polymerization catalyst.

  (E) A well-known substance can be used as a component. 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 an initiator.

  In addition to the components described above, the curable resin composition of the present invention is a trivinyl aromatic compound, trivinyl aliphatic compound, divinyl aliphatic compound, monovinyl aliphatic compound, monofunctional (meta) ) Other monomers such as acrylate esters and bifunctional (meth) acrylate esters can be used as the component (J).

  Specific examples of the other monomers include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, butadiene, isobornyl methacrylate, Bornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate Rate, dicyclopentanyl methacrylate, cyclohexane dimethanol diacrylate, dimethylol tricyclodecane diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclodecane dimethacrylate Rate, 1,4-butanediol diacrylate, hexanediol diacrylate, 1,4-butanediol dimethacrylate, although hexanediol dimethacrylate, and the like, but is not limited thereto. These can be used alone or in combination of two or more. The other monomers may be used within a range of less than 30% by weight of the total monomers.

In the curable resin composition of the present invention, a thickener can be blended as the component (H) as a component that increases the dispersibility of the filler and suppresses the sedimentation of the filler.
The thickener is not particularly limited, but polyvinyl alcohol, polyvinyl acetal, polyacrylic acid, fluorine-containing polymer, cellulose polymer, starch polymer, styrene polymer, acrylic polymer, styrene-acrylic acid. Conventionally known resins such as ester copolymers, polyamides, polyimides, and polyamideimides may be mentioned. Although these resin components can use a commercial item as it is, those derivatives prepared considering the solubility with respect to a solvent are more preferable.
The amount of thickener used is the total weight of the resin component (solid content excluding filler and solvent, including (A) to (C), (E), (F) and (J) components). Based on 0.2 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1.0 to 5.0% by weight.

  The curable resin composition of the present invention can be used as a coating solution without a solvent or by blending a solvent.

  The coating liquid of the present invention is obtained by dissolving the curable resin composition of the present invention with an aqueous solvent or an alcohol solvent. This coating liquid may contain a thickener as the component (H).

The curable resin composition of the present invention can be used in the absence of a solvent, but by adding an aqueous solvent, an alcohol solvent, or a mixed solvent thereof, the solid content concentration can be improved in coating workability and the like. It can select suitably in the range which does not impair.
The amount of the solvent used is in the range of 1 to 10000 parts by weight, preferably 10 to 1000 parts by weight, based on 100 parts by weight of the curable resin composition (excluding the solvent). The amount used is preferably changed according to the target viscosity.

  Examples of the aqueous solvent include water and a mixed solvent of water and an organic solvent compatible with water. Examples include an aqueous solution containing water and a surfactant, and the water content is 50% or more, preferably 70% or more. Preferred examples of the organic solvent compatible with water include alcohols.

  Examples of the alcohol solvent include methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, diacetone alcohol, furfuryl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, Examples thereof include alcohols such as 1,6-hexanediol and glycerin, or mixed solvents containing alcohols of 50% or more, preferably 70% or more. These alcohol solvents may be used alone or in combination of two or more.

In the aqueous solvent or alcohol solvent, other organic solvents can be dissolved and used within a range not impairing the effects of the present invention and within a range not causing phase separation.
Examples of other organic solvents include 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 Chain or cyclic ethers such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, acetylacetone and ethyl acetoacetate . Other organic solvents may be used alone or in combination of two or more.

  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.

It does not specifically limit as a preparation method of curable resin composition, It can prepare by mixing each component mentioned above. The order of addition of each component is not particularly limited. For example, each component such as components (A) to (C) and (F) is added to a slurry solution containing (D) a filler and a solvent, and a mixer is used. The curable resin composition can be prepared by mixing. As mixing and stirring, it is necessary to select a mixer that can stir to such an extent that no aggregate of filler remains in the slurry, and sufficient dispersion conditions as necessary. 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 (mixing operation of each component) of the curable resin composition of the present invention is preferably performed at least partly 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 coating film of the present invention is a coating film made of the curable resin composition of the present invention, and may be a coating film produced from the coating liquid.

  The coating film of the present invention is applied to the surface of a substrate such as a metal foil or a resin film by applying the curable resin composition of the present invention or a coating liquid containing the same, then removing the solvent and drying. Can be manufactured. The base material having the coating film of the present invention is excellent in adhesion between the base material and the coating film, and gives a functional coating film excellent in the functional properties imparted by the filler.

There is no restriction | limiting in particular as said base material, For example, alpha-olefins, such as polyethylene (PE), a polypropylene (PP), an ethylene propylene copolymer, an ethylene-vinyl acetate copolymer (EVA), are used as a monomer component. Olefin resins; Polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); Polyvinyl chloride (PVC); Vinyl acetate resins; Polyphenylene sulfide (PPS); Polyamide (nylon) ), Polyamide resins such as wholly aromatic polyamide (aramid); polyimide resins; various plastic materials such as polyetheretherketone (PEEK), rubber materials (for example, natural rubber, synthetic rubber, silicon rubber, etc.), metal materials (For example, alumini , 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, a plastic material substrate (plastic sheet, film, etc.) and a metal material (metal foil, punching metal, expanded metal, wire mesh, foam metal, mesh metal fiber sintered body, metal plated resin plate) are 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 curable resin composition. 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 curable resin composition is not particularly limited, but it is preferable that the thickness of the filler layer formed after removing the solvent is 0.001 to 5 mm, and 0.005 to 2 mm. It is more preferable to set it as an amount.

  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 soon 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 curing the curable resin composition of the present invention. For example, a cured product can be obtained by drying and curing the 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 60 ° C. or higher and 200 ° C. or lower for 1 second or longer and 60 minutes or shorter. If it is these conditions, the adhesiveness with respect to the base material of the coating film layer formed by fully bridge | crosslinking polymeric components, such as (A)-(C), (F) component in a coating film, and various uses It is possible to improve the functional properties of the filler layer against the above. When the heat treatment condition is less than 60 ° C. or less than 1 second, the adhesion property of the coating layer to the base material of the coating film layer and the functional property of the filler layer to the cured coating film may not be satisfied.

  The curable resin composition of the present invention can be made into a curable composite material by blending a reinforcing material such as carbon fiber or glass fiber if necessary. In 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 reinforcing material, 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, batteries such as lithium ion secondary batteries, and storage battery electrode materials such as 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 prepolymer Molecular weight and molecular weight distribution were measured using GPC (manufactured by Tosoh Corporation, HLC-8120GPC), tetrahydrofuran as a solvent, flow rate of 1.0 ml / min, column temperature of 38 ° C, calibration with monodisperse polystyrene. This was done using a line.

2) Prepolymer 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) Solvent solubility of prepolymer Soluble was evaluated by adding 5.0 g of solvent to 5.0 g of copolymer and stirring to dissolve the copolymer. This was left still, the presence or absence of insoluble matter such as gel was visually confirmed, and the case where no insoluble matter was observed was regarded as soluble.

In the following examples, each component used is as follows.
Monomer A: Methoxy-polyethylene glycol acrylate (Light acrylate 130A manufactured by Kyoeisha Chemical Co., Ltd.)
Monomer B: PEG400 # diacrylate (Light acrylate 9EG-A manufactured by Kyoeisha Chemical Co., Ltd.)
Oligomer C: Trimethylolpropane (EO) ₁₅ triacrylate (Miramer M3150, made by Miwon Specialty Chemical)
DVB-810: Mixture of 81% divinylbenzene and 19% ethylvinylbenzene (DVB-810, manufactured by Nippon Steel & Sumikin Chemical)
Thickener: Carboxymethylcellulose (CMC1120, manufactured by Daicel)
Initiator: 4,4'-azobis (4-cyanovaleric acid) (V-501, manufactured by Wako Pure Chemical Industries, Ltd.)
Antioxidant: Tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Adekastab AO-60, manufactured by ADEKA)

Synthesis example 1
Monomer A 0.16 mol (72.64 g), monomer B 0.036 mol (18.29 g), DVB-810 18.71 g (15.16 g of divinylbenzene and 3.55 g of ethylvinylbenzene), ethanol 518.21 g was put into a 1.0 L reactor, and an industrial pure product (purity 90%; manufactured by NOF Corporation) of 0.6 mmol of bis (4-t-butylcyclohexyl) peroxydicarbonate at 60 ° C. Parroyl TCP) was added to start the polymerization. The reaction was continued for 4 hours after the start of polymerization, and the polymerization solution was stopped with tert-butylcatechol. Then, it was devolatilized under reduced pressure at 60 ° C. to remove the remaining ethanol, and a prepolymer (copolymer) A solution was recovered.
Mn of the obtained prepolymer A was 11600, Mw was 18500, and Mw / Mn was 1.59. Residual vinyl groups present in the prepolymer A were quantified by performing ¹³ C-NMR and ¹ H-NMR analysis. As a result, the molar fraction of monomer units containing residual vinyl groups in all monomer units was 0.26. Prepolymer A was soluble in water, methanol, ethanol, isopropanol, THF, dichloroethane, dichloromethane, and chloroform at a concentration of 50 wt%, and no gel was observed.

Example 1
As the binder resin, the prepolymer A obtained in Synthesis Example 1 is used, and V-501 is used as a polymerization initiator, AO-60 is used as an antioxidant, CMC 1120 is used as a thickener, and carbon is used as a filler. The water-based conductive paint was prepared by adding 53 parts of ion exchange water as a solvent and kneading with a batch kneader for 30 minutes.
The carbon used as the filler was a mixture of 80 parts of graphite and 20 parts of carbon black.

Examples 2-5, Comparative Examples 1-2
The same method as in Example 1 except that the compounding recipe shown in Table 1 was used, and the monomer, polymerization initiator, and antioxidant were heated and mixed at 40 ° C. for 1 hour, prepolymerized, and then used for compounding. A conductive paint was obtained. Examples 2, 3, and 5 and Comparative Examples 1 and 2 used water as the solvent, and Example 4 used isopropanol as the solvent. Here, in the blending of Examples 2-5 and Comparative Examples 1-2, the prepolymer prepared by heating and mixing is soluble in a solvent such as water, ethanol, isopropanol, and butanol at a concentration of 50 wt%, No gel formation was observed. In Table 1, 0.08 part of DVB-810 contains 0.0648 part of divinylbenzene and 0.0152 part of ethylvinylbenzene.

  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.

In addition, the following method evaluated the characteristic of the coating material and its hardened | cured material.
4) 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.

5) 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.

6) Film strength: peel strength A water-based conductive paint is applied to a SUS plate with a doctor blade with a gap of 500 μm and dried at 90 ° C. for 1 hour. The strength was measured. It shows that the peel strength is good when it is 10 N or more.

7) Resistance value A coating film formed by applying an aqueous 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 can be said that the volume resistivity is good when it is 500 mΩcm or less.

8) Acid resistance: resistance value The SUS plate coated with the conductive paint obtained by the above-described evaluation of the film strength 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 can be said that the volume resistivity is good when it is 500 mΩcm or less.

9) Heat resistance: resistance value A sheet obtained by applying the conductive paint obtained by the above-described evaluation of the film strength and placing it in a 130 ° C air oven, leaving it for 120 hours, washing it with ion-exchanged water, and drying it. Similarly, the resistance value (volume resistivity) was measured. It can be said that the volume resistivity is good when it is 500 mΩcm or less.

Synthesis example 2
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.

Example 6
Ethanol solution 2 obtained by mixing 0.68 g of monomer B, 0.30 g of oligomer C, 0.02 g of DVB-810, 0.01 g of V-501, and 1.5 g of ethanol and polymerizing to prepolymerize. 0.5 g and 50 g of methanol sol in which the iron oxide / titanium oxide composite oxide fine particles obtained in Synthesis Example 2 were dispersed were mixed to prepare a coating solution for forming a transparent film.

  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 4H in pencil hardness.

Place the above coated substrate into 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. Black light (ultraviolet wavelength: 365 nm, intensity: 0.6 mW / cm ² ) was irradiated for 1 hour from a height of 100 mm. Next, when the concentration of acetaldehyde remaining in the container was measured by gas chromatography, it was 10.5 ppm. Therefore, when the photocatalytic activity was evaluated based on the reduction rate of acetaldehyde, the photocatalytic activity was 79%. The physical properties such as filler dispersibility and heat resistance were also excellent.

Claims (10)

(1) The following component (A), component (B), component (C), and component (D),
(2) One or more components selected from the following (A) component, (B) component, and (C) component, the following (F) component, and (D) component, or (3) the following (F) component, and (D) component,
A curable resin composition comprising:
The component (A) is represented by the diacrylate compound (a1) having a polyether structure represented by the following formula (I), or the diacrylate compound (a1) and the following formula (II) or the following formula (III). An acrylate compound having a polyether structure (a2),

Wherein R ¹ and R ² are hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, or halogen, R ³ is hydrogen, and R ⁴ is hydrogen or alkyl having 1 to 4 carbon atoms. And m is an integer of 3 to 20.)

(Wherein R ⁵ is hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, or halogen, and R ⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms. An aryl group of 6 to 30, R ⁷ is hydrogen, and R ⁸ is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 3 to 50.)

Wherein R ¹⁰ is hydrogen, R ¹¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, Y is hydrogen, an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, aryl A group, an acryloyl group or a methacryloyl group, and at least one of Y is an acryloyl group or a methacryloyl group, and p is an integer of 1 to 50, but at least one of p satisfies 3 <p ≦ 50. Z is an active hydrogen compound residue, and q is an integer of 1 to 6.)
(B) component is a divinyl aromatic compound,
(C) component is a monovinyl aromatic compound,
(D) component is a filler,
The component (F) is a prepolymer derived from the components (A), (B) and (C);
(A) component, (B) component, (C) component, and (F) component when the sum total is 100 weight part, (A) component is 50-99.9 weight part, (B) component is 0 0.05 to 25 parts by weight, (C) component is 0.05 to 25 parts by weight, (D) component is 20 to 20,000 parts by weight (provided that (F) component is included, (F) The units derived from the component (A), the component (B), and the component (C) in the unit constituting the component are calculated as the component (A), the component (B), and the component (C), respectively).
And the curable resin composition is used without a solvent, or is used together with an aqueous solvent or an alcohol solvent.   The curable resin composition of Claim 1 containing (A) component, (B) component, (C) component, and (D) component.   The curable resin composition according to claim 1, comprising a component (F) and a component (D).   2. The curable resin composition according to claim 1, comprising at least one component selected from the component (A), the component (B), and the component (C), the component (F), and the component (D).   (E) The curable resin composition in any one of Claims 1-4 containing a polymerization initiator as a component.   The curable resin composition according to any one of claims 1 to 5, wherein the acrylate compound (a2) in the component (A) is an acrylate compound having a polyether structure represented by the formula (II).   A coating liquid comprising the curable resin composition according to claim 1 dissolved in an aqueous solvent or an alcohol solvent.   The coating liquid according to claim 7 containing a thickener as component (H).   The coating film which consists of a curable resin composition in any one of Claims 1-6. Hardened | cured material of the curable resin composition in any one of Claims 1-6.