WO2023182495A1 - Curable resin composition - Google Patents

Curable resin composition Download PDF

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Publication number
WO2023182495A1
WO2023182495A1 PCT/JP2023/011812 JP2023011812W WO2023182495A1 WO 2023182495 A1 WO2023182495 A1 WO 2023182495A1 JP 2023011812 W JP2023011812 W JP 2023011812W WO 2023182495 A1 WO2023182495 A1 WO 2023182495A1
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WO
WIPO (PCT)
Prior art keywords
epoxy compound
curable resin
resin composition
molecule
ester bond
Prior art date
Application number
PCT/JP2023/011812
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French (fr)
Japanese (ja)
Inventor
脩平 ▲高▼嶋
悠斗 小田桐
Original Assignee
太陽ホールディングス株式会社
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Application filed by 太陽ホールディングス株式会社 filed Critical 太陽ホールディングス株式会社
Publication of WO2023182495A1 publication Critical patent/WO2023182495A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1525—Four-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents

Definitions

  • the present invention relates to a curable resin composition.
  • a light shielding member for a display mounted on a PC or a mobile device is required to have high light shielding properties because it is necessary to suppress the influence of backlight as much as possible. Therefore, a light-shielding ink for forming a black matrix is used as a material for such a light-shielding member.
  • a technique of manufacturing a light shielding member by applying such a light shielding ink to a substrate using an inkjet method is attracting attention.
  • Patent Document 1 discloses an active energy ray-curable ink containing a photocationic polymerization initiator, a polyfunctional epoxy compound, a monofunctional alicyclic epoxy compound, and an oxetane compound. , has proposed a technology for use in inkjet recording.
  • smartphones and smart watches are expected to be used not only at room temperature but also in various environments such as in the summer and inside cars, so it is desirable that the light-shielding ink used has high reliability. It will be done. For example, it must not only have high light blocking properties, but also maintain high adhesion to the substrate even under high temperature and high humidity conditions, have good curability, and the cured coating that is formed after curing. It is also essential for light-shielding inks to have high hardness.
  • light-shielding inks usually contain pigments for light-shielding purposes at a high concentration, and are characterized by a high OD value. Therefore, when applying light-shielding ink to a substrate using the inkjet method, there is a phenomenon in which the light used to photocure the light-shielding ink coating formed on the substrate has difficulty reaching the bottom of the coating. It inevitably happens. As a result, the curability of the entire coating film is insufficient, resulting in a problem that the hardness of the cured coating film itself and its adhesion to a substrate such as glass or metal are impaired.
  • the active energy ray-curable ink proposed in Patent Document 1 uses an alicyclic epoxy compound having an ester bond in the molecule, when the pigment concentration is increased, the coating film It is assumed that it is difficult for light to sufficiently reach the bottom. Therefore, the curing properties of the coating film are not sufficient, and it is difficult to maintain the adhesion of the cured coating film to the substrate when left under high temperature and high humidity conditions. It is expected that the hardness of the cured coating will also not meet the required standards.
  • the object of the present invention is to provide a curable resin composition that provides a highly cured coating film.
  • the present invention contains two types of epoxy compounds each having structural characteristics in a mass ratio within a specific numerical range, and further contains an oxetane compound, a photoacid generator, and a black colorant.
  • the inventors have discovered that the above problems can be solved by employing a curable resin composition, and have completed the present invention.
  • a curable resin composition comprising (A) an epoxy compound, (B) an oxetane compound, (C) a photoacid generator, and (D) a black colorant,
  • the epoxy compound (A) is (a) an alicyclic epoxy compound having an ester bond in the molecule and (b) an alicyclic epoxy compound having no ester bond in the molecule at a mass ratio in the numerical range of 5:100 to 30:100.
  • the curable resin composition of the present invention can be applied to an inkjet method.
  • the viscosity is preferably in the range of 5 to 20 mPa ⁇ s at 50°C, and preferably in the range of 5 to 15 mPa ⁇ s at 50°C. It is more preferable that it is within the range.
  • the viscosity can be measured using, for example, a cone plate viscometer (TVE-33H manufactured by Toki Sangyo Co., Ltd.).
  • a more preferred embodiment relates to a curable resin composition in which the alicyclic epoxy compound (b) having no ester bond in the molecule has a difunctional epoxy group.
  • the black colorant (D) is carbon black and is contained in an amount of 5 parts by mass or more based on a total of 100 parts by mass of the epoxy compound (A) and the oxetane compound (B).
  • the present invention relates to a synthetic resin composition.
  • Another preferred embodiment relates to a curable resin composition in which the mass ratio of the oxetane compound (B) to the epoxy compound (A) is in the numerical range of 2:100 to 40:100.
  • the epoxy compound (A) comprises (a) an alicyclic epoxy compound having an ester bond in the molecule, and (b) an alicyclic epoxy compound having no ester bond in the molecule. , in a mass ratio in the numerical range of 8:100 to 25:100. (a) By specifying the blending ratio of the alicyclic epoxy compound having an ester bond in the molecule within the above range, a cured coating film with excellent adhesion even after being left in high temperature and high humidity conditions is produced. be able to.
  • Another preferred embodiment relates to a curable resin composition in which the mass ratio of the oxetane compound (B) to the epoxy compound (A) is in the numerical range of 10:100 to 20:100.
  • B By regulating the blending ratio of the oxetane compound within the above range, the curability of the surface and bottom of the coating film can be improved in a well-balanced manner. By setting the ratio of the above-mentioned amount to be equal to or higher than the lower limit, the tackiness of the cured coating film after photocuring will be good.
  • the crosslinking density of the cured coating film can be maintained at an appropriate level, flexibility can be maintained, and the pencil hardness and adhesion after being left in high temperature and high humidity conditions can be improved.
  • Yet another preferred embodiment also relates to a curable resin composition that further contains an alkoxyanthracene derivative as a photosensitizer.
  • the OD value of the cured coating film at a film thickness of 10 to 20 ⁇ m is preferably 4 or more. , more preferably 5 or more.
  • the curable resin composition of the present invention having the above configuration not only has high light-shielding properties, but also has good curability on the surface of the coating film, and exhibits stable adhesion even under high temperature and high humidity conditions. It also has the excellent advantage of forming a cured coating film with high hardness. Furthermore, since the curable resin composition of the present invention is suitable for inkjet applications, it also has the advantage of good production efficiency in the production of various displays.
  • the curable resin composition of the present invention is also expected to be particularly suitable for use as a black light-shielding material for displays, for example, due to the above-mentioned properties.
  • the curable resin composition of the present invention contains (A) an epoxy compound in order to increase the hardness of the cured product (cured coating film) to be formed.
  • the curable resin composition of the present invention contains the (a) epoxy compound in the molecule in order to improve adhesion to the base material even when exposed to harsh environments of higher temperature and humidity. Two types of epoxy compounds are used together: an alicyclic epoxy compound having an ester bond, and (b) an alicyclic epoxy compound having no ester bond in the molecule.
  • an alicyclic epoxy compound is usually employed as one of the epoxy compounds due to its high reactivity.
  • an alicyclic epoxy compound having an ester bond it is customary to employ an alicyclic epoxy compound having an ester bond.
  • adhesion to the base material is not sufficient.
  • the present invention provides two epoxy compounds: (a) an alicyclic epoxy compound having an ester bond in the molecule; and (b) an alicyclic epoxy compound having no ester bond in the molecule.
  • a curable resin composition is prepared in which two kinds of epoxy compounds are used in combination, and in addition, these two kinds of epoxy compounds are mixed in a mass ratio in a numerical range of 5:100 to 30:100, preferably 8:100 to 25:100. By including it in the above, the above-mentioned disadvantages can be avoided.
  • an alicyclic epoxy compound having an ester bond in the molecule has one or more aliphatic ring structures in the molecule, and two carbon atoms and an oxygen atom in the aliphatic ring form an epoxy group. It refers to a compound with the following structure. And (a) the alicyclic epoxy compound having an ester bond in the molecule refers to a compound in which the above-mentioned alicyclic epoxy compound further has an ester bond in its chemical structure.
  • each compound having the following structure (In the formula, n1 represents an integer from 1 to 30) (In the formula, A represents an alkylene group having 1 to 8 carbon atoms; n2 represents an integer of 1 to 30) are preferred.
  • the alicyclic epoxy compound having an ester bond in the molecule may be used alone or in combination of two or more.
  • an alicyclic epoxy compound that does not have an ester bond in the molecule refers to the alicyclic epoxy compound described in the section of (a) the alicyclic epoxy compound that has an ester bond in the molecule above. However, it refers to a compound that does not have an ester bond in its molecule, such as an alicyclic epoxy compound that has an ether bond instead of an ester bond.
  • Examples of alicyclic epoxy compounds that do not have an ester bond in the molecule include compounds having the following structure: can be mentioned.
  • alicyclic epoxy compounds (b) having no ester bond in the molecule those having a difunctional epoxy group are more preferred in the present invention.
  • Such (b) alicyclic bifunctional epoxy compound having no ester bond in the molecule has the following structural formula in the molecule: Ethylene oxide group represented by and/or the following structural formula: It is a compound having a total of two cyclohexene oxide groups represented by Commercially available products include, for example, THI-DE, DE-102 and DE-103 (manufactured by JXTG Energy Corporation), and X-40-2678 and X-40-2669 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the alicyclic epoxy compound having no ester bond in the molecule may be used alone or in combination of two or more.
  • the total content of (a) the alicyclic epoxy compound having an ester bond in the molecule in the curable resin composition of the present invention is determined from the viewpoints of curability and tackiness. It is preferably 3 to 60 parts by weight, more preferably 3 to 30 parts by weight, based on a total of 100 parts by weight of the compound.
  • the total content of (b) alicyclic epoxy compound that does not have an ester bond in the molecule is 100 parts by mass in total of (A) epoxy compound and (B) oxetane compound from the viewpoint of adhesion to the base material.
  • it is preferably 30 to 90 parts by weight, more preferably 40 to 80 parts by weight.
  • the respective contents of these two types of alicyclic epoxy compounds (a) and (b) need to be adjusted to a ratio within the specific numerical range as already described above.
  • the curable resin composition of the present invention comprises (a) an alicyclic epoxy compound having an ester bond in the molecule and (b) an alicyclic epoxy compound having no ester bond in the molecule, as well as
  • the epoxy compound (A) epoxy compounds other than (a) and (b), such as non-alicyclic epoxy
  • the other epoxy compounds that can be used in the present invention are commonly used, they are not all listed here, but preferable ones include Denacol EX-212 and Denacol EX-121 ( (all manufactured by Denacol), and KBM-403 (manufactured by Shin-Etsu Silicone).
  • the total content is the total of (A) epoxy compounds (including the epoxy compounds of (a) and (b) and other epoxy compounds) and (B) oxetane compounds (100 It is preferably 130 parts by weight, more preferably 3 to 20 parts by weight.
  • (B) Oxetane compound In the curable resin composition of the present invention, (B) an oxetane compound is contained as a thermosetting resin from the viewpoint of improving the hardness of the cured product.
  • the content of the (B) oxetane compound is the total amount of the above (A) epoxy compound, that is, (a) an alicyclic epoxy compound having an ester bond in the molecule; The mass ratio is adjusted to be within a specific numerical range with respect to the total amount of the alicyclic epoxy compound and other epoxy compounds that do not have an ester bond therein.
  • the content of the (B) oxetane compound is preferably such that the mass ratio of the (B) oxetane compound to the (A) epoxy compound is in the numerical range of 2:100 to 40:100. is adjusted to have a numerical value range of 10:100 to 20:100.
  • the oxetane compound (B) is not limited to monofunctional ones, but polyfunctional ones can also be used.
  • Examples of the monofunctional oxetane compound (B) include 3-methyloxetane, 3-ethyloxetane, 3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, and 3-ethyl-3-hydroxymethyloxetane. Can be mentioned.
  • polyfunctional oxetane compound (B) bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3- Oxetane Examples include etherification products of alcohols with novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, or resins having hydroxyl groups such as silsesquioxane. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth)acrylates.
  • oxetane compound (B) It is of course possible to use a commercially available product as the oxetane compound (B).
  • OXT-101, OXT-121, OXT-212 and OXT-221 are preferred.
  • the curable resin composition of the present invention may contain one or more of the above (B) oxetane compounds.
  • the content of the oxetane compound (B) is preferably 3 to 40 parts by mass, and 8 to 30 parts by mass, based on the total of 100 parts by mass of the epoxy compound (A) and the oxetane compound (B), from the viewpoint of the hardness of the cured product. Parts by mass are more preferred. However, the content of the (B) oxetane compound needs to be adjusted so that the mass ratio to the mass of the contained (A) epoxy compound falls within the specific numerical range as described above.
  • the total amount of the epoxy compound (A) and the oxetane compound (B) is preferably 25 to 95% by mass, more preferably 35 to 90% by mass, based on the mass of the curable resin composition of the present invention.
  • the curable resin composition of the present invention contains (C) a photoacid generator as a compound capable of generating a substance that initiates cationic polymerization upon irradiation with ultraviolet rays.
  • C) Photoacid generators include, for example, onium salts such as diazonium salts, iodonium salts, bromonium salts, chloronium salts, sulfonium salts, selenonium salts, pyrylium salts, thiapyrylium salts, and pyridinium salts; tris(trihalomethyl)-s -halogenated compounds such as triazines and their derivatives; 2-nitrobenzyl esters of sulfonic acids; iminosulfonates; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivatives; N-hydroxyimidosulfonates; tri(methanesulfonyloxy) ) benzen
  • C Commercially available products can be used as the photoacid generator, such as CPI-100P, CPI-200K, CPI-101A (manufactured by Sun-Apro), Cylacure photocuring initiator UVI-6990, Cylacure photocuring Initiator UVI-6992, Silacure photocuring initiator UVI-6976 (manufactured by Dow Chemical Japan Co., Ltd.), ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-152, ADEKA OPTOMER SP-170, ADEKA OPTOMER SP -172 (manufactured by Asahi Denka Kogyo Co., Ltd.), CI-5102, CI-2855 (manufactured by Nippon Soda Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, Sun-Aid SI -180L, SunAid
  • CPI-100P, CPI-101A, CPI-200K, CPI-210S, or aromatic iodonium salts Omnicat 250, WPI-113, WPI-116, WPI-169 and WPI-170 are preferred.
  • the content of the photoacid generator (C) in the curable resin composition is preferably 5 to 30 parts by mass, and more preferably, It is 7 to 15 parts by mass.
  • the curable resin composition of the present invention preferably contains (D) a black colorant, particularly a black pigment, from the viewpoint that it is usually used for black light shielding.
  • black pigments such as carbon black are preferably used, but black dyes and other coloring agents may also be used within a range that does not deviate greatly from the viewpoint of the intended use, or in addition to carbon black. Of course, it may be further contained.
  • black pigments include, in addition to carbon black, inorganic pigments such as triiron tetroxide (Fe 3 O 4 ), black titanium oxide, copper manganese black, copper chrome black, and cobalt black, and cyanine black and aniline black.
  • inorganic pigments such as triiron tetroxide (Fe 3 O 4 ), black titanium oxide, copper manganese black, copper chrome black, and cobalt black, and cyanine black and aniline black.
  • organic pigments include organic pigments.
  • colorants having other colors include known and commonly used red, blue, green, and yellow pigments or dyes.
  • the content of the black colorant (D) in the curable resin composition of the present invention is adjusted in consideration of the use of the cured product to be formed, but from the viewpoint of the balance between curability and adhesion of the coating film, ( The content is preferably 5 parts by mass or more, more preferably 5 parts by mass or more and 15 parts by mass or less, based on a total of 100 parts by mass of A) the epoxy compound and (B) the oxetane compound.
  • the curable resin composition of the present invention preferably further contains a photosensitizer in order to further increase photosensitivity.
  • the photosensitizer is preferably a compound that becomes excited by light with a wavelength of 350 nm to 450 nm.
  • Examples include polynuclear aromatics such as pyrene, perylene, triphenylene, and anthracene; xanthenes such as fluorescein, eosin, erythrosin, rhodamine B, and rose bengal; xanthone such as xanthone, thioxanthone, dimethylthioxanthone, and diethylthioxanthone; Cyanines such as carbocyanine and oxacarbocyanine; merocyanines such as merocyanine and carbomerocyanine; rhodacyanines; oxonols; thiazines such as thionine, methylene blue and toluidine blue; acridines such as acridine orange, chloroflavin and acriflavin ; acridones such as acridone and 10-butyl-2-chloroacridone; anthraquinones;
  • UVS-1101 diethoxyanthracene; manufactured by Kawasaki Chemical Industries, Ltd.
  • Anthracure registered trademark
  • UVS-1221 dipropoxyanthracene; manufactured by Kawasaki Chemical Industries, Ltd.
  • alkoxyanthracene derivatives such as Anthracure (registered trademark) UVS-1331 (dibutoxyanthracene; manufactured by Kawasaki Chemical Industries, Ltd.).
  • the content of the photosensitizer is 0.1 to 2.0 parts by mass, preferably 0.2 to 1.0 parts by mass, per 1 part by mass of the photoacid generator.
  • the curable resin composition of the present invention may contain, for example, a solvent, a reactive diluent, a dispersant, a thickener, a surfactant, an antioxidant, a plasticizer, a flame retardant, within a range that does not impair its properties.
  • Other components such as antistatic agents, leveling agents, antifoaming agents, and antibacterial agents may also be contained.
  • a photoreactive diluent is preferable.
  • photoreactive diluents include (meth)acrylates, vinyl ethers, ethylene derivatives, styrene, chloromethylstyrene, ⁇ -methylstyrene, maleic anhydride, dicyclopentadiene, N-vinylpyrrolidone, N-vinylformamide, and xylene.
  • examples include compounds having an unsaturated double bond, an oxetanyl group, and an epoxy group, such as dioxetane, oxetane alcohol, 3-ethyl-3-(phenoxymethyl)oxetane, and resorcinol diglycidyl ether.
  • (meth)acrylates are preferred.
  • the curable resin composition of the present invention is applied to a target location on a substrate by an inkjet method, and is cured to form a cured product.
  • a suitable inkjet printing method is an on-demand piezo method, but the method is not particularly limited.
  • Suitable wavelengths include 365 nm, 385 nm, 395 nm, 405 nm, etc. in the ultraviolet region, but are not particularly limited. Curing is performed by irradiating the applied composition with active energy radiation.
  • Suitable light sources for irradiating active energy rays include LEDs, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, and the like.
  • electron beams, ⁇ rays, ⁇ rays, ⁇ rays, X rays, neutron beams, etc. can also be used.
  • the number of irradiation light sources is one or two or more, and in the case of two or more, it is of course possible to use a combination of light sources of different wavelengths.
  • the amount of exposure to active energy rays is usually in the range of 10 to 10,000 mJ/cm 2 , preferably 20 to 2,000 mJ/cm 2 , and more preferably 100 to 2,000 mJ/cm 2 .
  • each component was blended and premixed using a stirrer to prepare curable resin compositions for Examples 1 to 10 and Comparative Examples 1 to 4.
  • the numerical values of the blending amounts in the table indicate parts by mass unless otherwise specified.
  • curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 cured products (cured coating films) with a film thickness of 5 ⁇ m were obtained, and the cured products were subjected to cross-cutting, pencil cutting, etc. as described below. Hardness and dryness to touch after UV curing were measured.
  • the viscosity of the curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 was determined by measuring the viscosity at an ink temperature of 50°C and 100 rpm using a cone plate viscometer (TVE-33H manufactured by Toki Sangyo Co., Ltd.). However, in all cases, the pressure was in the range of 5 to 20 mPa ⁇ s.
  • the cross-cuts were made after being left at 23°C and 50% RH for 3 hours (initial adhesion) and after being placed in a constant temperature and humidity chamber (Espec LHL-114) under the conditions of 85°C and 85% relative humidity. ) and after standing for 240 hours (85° C., 85% RH in close contact).
  • the evaluation criteria are as follows.
  • the evaluation criteria other than " ⁇ " and "x" indicate that the adhesion between the cured coating film and the test substrate is good, and the evaluation criteria of " ⁇ " indicates that the adhesion is particularly good.
  • ⁇ The grid remains 100% adhered after peeling, and no chipping is observed.
  • ⁇ The grid remains 100% adhered after peeling, and slight chipping is observed at the intersection of the grids.
  • ⁇ The squares after peeling remain 100% attached, and peeling occurs at the intersections of the squares.
  • Table 2 The results are shown in Table 2 below.
  • the OD value of each Example and each Comparative Example with a film thickness of 10 ⁇ m after curing was 4 or more and 6 or less
  • the OD value of each Example and each Comparative Example with a film thickness of 20 ⁇ m after curing was 6 or more.
  • the OD value was sufficient for use as a black light shielding agent.
  • the film thickness after curing 10 ⁇ m or 20 ⁇ m was formed by drawing on an inkjet printer every 5 ⁇ m using the same method as in [Preparation of test substrate], then curing with UV, and stacking up to a predetermined film thickness. It is.
  • the mass ratio of (a) an alicyclic epoxy compound having an ester bond in the molecule and (b) an alicyclic epoxy compound having no ester bond in the molecule is in a more preferable range of 8:100 to 25: 100, and the mass ratio of the (B) oxetane compound and the (A) epoxy compound was set to a more preferable range of 10:100 to 20:100.
  • Example 1 Example 3, Example 5, Example 6 had the best results among the evaluation criteria. In particular, the results were better than other examples in terms of cross-cutting (85° C., 85% RH adhesion) and pencil hardness under high temperature and high humidity conditions.
  • the mass ratio of (a) an alicyclic epoxy compound having an ester bond in the molecule and (b) an alicyclic epoxy compound having no ester bond in the molecule is outside the range of 43:100 to 50. :100
  • Comparative Example 3 which does not contain an alicyclic epoxy compound having an ester bond in the molecule (a) was slightly inferior in cross-cut (initial adhesion) and Regarding cross-cutting under high humidity conditions (adhesion at 85° C. and 85% RH), the cured coating film peeled off, resulting in the worst result among the evaluation criteria.
  • Comparative Examples 1 to 3 had the worst results in terms of pencil hardness among the evaluation criteria.
  • Comparative Example 4 had good cross-cut evaluation results, but pencil hardness and tack had the worst results among the evaluation criteria.

Abstract

[Problem] To provide a curable resin composition for black light shielding for an inkjet, the curable resin composition having excellent surface curability in addition to high light-shielding properties, exhibiting stable adhesion under high-temperature and high-humidity conditions, and yielding a cured coating film having high hardness after curing. [Solution] A curable resin composition containing (A) an epoxy compound, (B) an oxetane compound, (C) a photoacid generator, and (D) a black colorant, wherein the (A) epoxy compound contains (a) an alicyclic epoxy compound having an ester bond in each molecule and (b) an alicyclic epoxy compound not having an ester bond in each molecule in a mass ratio within a numerical range of 5:100-30:100. [Selected drawing] None

Description

硬化性樹脂組成物Curable resin composition
　本発明は、硬化性樹脂組成物に関する。 The present invention relates to a curable resin composition.
　ＰＣあるいはモバイルデバイスに搭載されるディスプレイの遮光部材においては、バックライトの影響をできる限り抑える必要があるため、高い遮光性が要求される。このため、そのような遮光部材の材料としてブラックマトリックスを形成するための遮光インキが用いられる。また一方では、製造効率の観点から、インクジェット法を用いて、そのような遮光インキを基板に塗布して遮光部材を製造するという技術が注目されている。
　インクジェット法を用いてインクを対象に塗布する技術として、例えば特許文献１は、光カチオン重合開始剤、多官能エポキシ化合物、単官能脂環式エポキシ化合物およびオキセタン化合物を含む活性エネルギー線硬化型インクを、インクジェット記録に用いるという技術を提案している。 A light shielding member for a display mounted on a PC or a mobile device is required to have high light shielding properties because it is necessary to suppress the influence of backlight as much as possible. Therefore, a light-shielding ink for forming a black matrix is used as a material for such a light-shielding member. On the other hand, from the viewpoint of manufacturing efficiency, a technique of manufacturing a light shielding member by applying such a light shielding ink to a substrate using an inkjet method is attracting attention.
As a technique for applying ink to a target using an inkjet method, for example, Patent Document 1 discloses an active energy ray-curable ink containing a photocationic polymerization initiator, a polyfunctional epoxy compound, a monofunctional alicyclic epoxy compound, and an oxetane compound. , has proposed a technology for use in inkjet recording.
特開２０１０－１０６２５４号公報Japanese Patent Application Publication No. 2010-106254
　ここで、特にスマートフォンやスマートウォッチは、常温での使用の他、夏場や車内など様々な環境で使用されることが当然想定されるため、用いられる遮光インクとしては高い信頼性を有することが望まれる。例えば、高い遮光性はもちろんのこと、高温高湿下でも基材との密着性が高く維持されるものであること、硬化性が良好であること、および、その硬化後に形成される硬化塗膜が高い硬度を有すること、もまた遮光インクには必須である。 In particular, smartphones and smart watches are expected to be used not only at room temperature but also in various environments such as in the summer and inside cars, so it is desirable that the light-shielding ink used has high reliability. It will be done. For example, it must not only have high light blocking properties, but also maintain high adhesion to the substrate even under high temperature and high humidity conditions, have good curability, and the cured coating that is formed after curing. It is also essential for light-shielding inks to have high hardness.
　ところが、通常、遮光インクには遮光用途の顔料が高濃度で添加されており、そのＯＤ値が高いという特徴を有する。そのため、インクジェット法を用いて遮光インクを基材に塗布しようとすると、基材上に形成した遮光インクの塗膜を光硬化させるための光が、当該塗膜の底部まで到達しにくいという現象が必然的に発生する。その結果、塗膜全体の硬化性が不足して、硬化塗膜自体の硬度、および、ガラスもしくは金属などの基材への密着性が損なわれてしまうという課題を生じる。 However, light-shielding inks usually contain pigments for light-shielding purposes at a high concentration, and are characterized by a high OD value. Therefore, when applying light-shielding ink to a substrate using the inkjet method, there is a phenomenon in which the light used to photocure the light-shielding ink coating formed on the substrate has difficulty reaching the bottom of the coating. It inevitably happens. As a result, the curability of the entire coating film is insufficient, resulting in a problem that the hardness of the cured coating film itself and its adhesion to a substrate such as glass or metal are impaired.
　この点において、特許文献１が提案する活性エネルギー線硬化型インクにあっては、分子内にエステル結合を有する脂環式エポキシ化合物が使用されているものの、顔料濃度を高くした場合に、塗膜底部まで光が十分に到達しにくいことが想定される。そのため、塗膜の硬化性が十分ではなく、また、高温高湿条件下で放置した際の硬化塗膜の基材への密着性を保持することが容易でなく、且つ、インクの硬化後の硬化塗膜の硬度もまた、要求される水準を満たし得ないことが予測される。 In this regard, although the active energy ray-curable ink proposed in Patent Document 1 uses an alicyclic epoxy compound having an ester bond in the molecule, when the pigment concentration is increased, the coating film It is assumed that it is difficult for light to sufficiently reach the bottom. Therefore, the curing properties of the coating film are not sufficient, and it is difficult to maintain the adhesion of the cured coating film to the substrate when left under high temperature and high humidity conditions. It is expected that the hardness of the cured coating will also not meet the required standards.
　そこで、以上の観点に鑑みて、本発明においては、高い遮光性に加えて、表面硬化性が良好であり、高温高湿条件での安定した密着性を発揮するとともに、且つ硬化後の硬度も高い硬化塗膜を与える硬化性樹脂組成物を提供することを課題とした。 Therefore, in view of the above points, in the present invention, in addition to high light-shielding properties, surface hardening properties are good, and stable adhesion is exhibited under high temperature and high humidity conditions, and the hardness after curing is also low. The object of the present invention is to provide a curable resin composition that provides a highly cured coating film.
　本発明者は鋭意検討の結果、構造的にそれぞれ特徴ある２種のエポキシ化合物を特定の数値範囲の質量比にて含み、さらに、オキセタン化合物と、光酸発生剤と、黒色着色剤とを含む硬化性樹脂組成物を採用したことによって、上記課題を解決し得ることを見出し、本発明を完成するに至った。
　即ち、当該課題は、より具体的には、
　（Ａ）エポキシ化合物と、（Ｂ）オキセタン化合物と、（Ｃ）光酸発生剤と、（Ｄ）黒色着色剤とを含む硬化性樹脂組成物であって、
　前記（Ａ）エポキシ化合物は、
（ａ）分子内にエステル結合を有する脂環式エポキシ化合物と、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物とを、５：１００～３０：１００の数値範囲の質量比で含む、
前記硬化性樹脂組成物
によって解決され得る。 As a result of intensive studies, the present inventor found that the present invention contains two types of epoxy compounds each having structural characteristics in a mass ratio within a specific numerical range, and further contains an oxetane compound, a photoacid generator, and a black colorant. The inventors have discovered that the above problems can be solved by employing a curable resin composition, and have completed the present invention.
That is, the problem is more specifically,
A curable resin composition comprising (A) an epoxy compound, (B) an oxetane compound, (C) a photoacid generator, and (D) a black colorant,
The epoxy compound (A) is
(a) an alicyclic epoxy compound having an ester bond in the molecule and (b) an alicyclic epoxy compound having no ester bond in the molecule at a mass ratio in the numerical range of 5:100 to 30:100. include,
This problem can be solved by the above-mentioned curable resin composition.
　本発明の硬化性樹脂組成物は、インクジェット工法に適用することができる。その場合、より好ましい態様は、インクジェットノズルからの円滑な吐出の観点から、その粘度は、５０℃にて５～２０ｍＰａ・ｓの範囲にあるのが好ましく、５０℃にて５～１５ｍＰａ・ｓの範囲にあるのがより好ましい。
　粘度は、例えば、コーンプレート型粘度計（東機産業社製ＴＶＥ－３３Ｈ）を用いて測定し得る。 The curable resin composition of the present invention can be applied to an inkjet method. In that case, from the viewpoint of smooth ejection from the inkjet nozzle, the viscosity is preferably in the range of 5 to 20 mPa·s at 50°C, and preferably in the range of 5 to 15 mPa·s at 50°C. It is more preferable that it is within the range.
The viscosity can be measured using, for example, a cone plate viscometer (TVE-33H manufactured by Toki Sangyo Co., Ltd.).
　より好ましい態様は、前記（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物は、２官能のエポキシ基を有する、硬化性樹脂組成物に関する。 A more preferred embodiment relates to a curable resin composition in which the alicyclic epoxy compound (b) having no ester bond in the molecule has a difunctional epoxy group.
　また別の好ましい態様は、前記（Ｄ）黒色着色剤が、カーボンブラックであり、かつ前記（Ａ）エポキシ化合物と（Ｂ）オキセタン化合物の合計１００質量部に対して５質量部以上含まれる、硬化性樹脂組成物に関する。 In another preferred embodiment, the black colorant (D) is carbon black and is contained in an amount of 5 parts by mass or more based on a total of 100 parts by mass of the epoxy compound (A) and the oxetane compound (B). The present invention relates to a synthetic resin composition.
　また別の好ましい態様は、前記（Ｂ）オキセタン化合物と、前記（Ａ）エポキシ化合物との質量比が、２：１００～４０：１００の数値範囲にある、硬化性樹脂組成物に関する。 Another preferred embodiment relates to a curable resin composition in which the mass ratio of the oxetane compound (B) to the epoxy compound (A) is in the numerical range of 2:100 to 40:100.
　また別の好ましい態様は、前記（Ａ）エポキシ化合物は、（ａ）分子内にエステル結合を有する脂環式エポキシ化合物と、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物とを、８：１００～２５：１００の数値範囲の質量比で含む、硬化性樹脂組成物に関する。（ａ）分子内にエステル結合を有する脂環式エポキシ化合物の配合量の比率を上記の範囲で規定することで、高温高湿条件に放置した後でも密着性に優れた硬化塗膜を作製することができる。（ａ）分子内にエステル結合を有する脂環式エポキシ化合物の配合量を上記質量比の下限以上とすることで、エステル結合の加水分解による塗膜の柔軟性を適度に保って、塗膜の内部応力を抑制し、初期密着性を向上できると想定される。また、（ａ）分子内にエステル結合を有する脂環式エポキシ化合物の配合量を上記質量比の上限以下とすることで、高温高湿条件に放置した後に塗膜が加水分解を経ることによる塗膜の劣化を抑制して、密着性等の光硬化後の塗膜物性を維持することができると想定される。 In another preferred embodiment, the epoxy compound (A) comprises (a) an alicyclic epoxy compound having an ester bond in the molecule, and (b) an alicyclic epoxy compound having no ester bond in the molecule. , in a mass ratio in the numerical range of 8:100 to 25:100. (a) By specifying the blending ratio of the alicyclic epoxy compound having an ester bond in the molecule within the above range, a cured coating film with excellent adhesion even after being left in high temperature and high humidity conditions is produced. be able to. (a) By setting the blending amount of the alicyclic epoxy compound having an ester bond in the molecule to the lower limit of the above mass ratio or more, the flexibility of the coating film due to hydrolysis of the ester bond can be maintained appropriately, and the coating film can be improved. It is assumed that internal stress can be suppressed and initial adhesion can be improved. In addition, (a) by setting the blending amount of the alicyclic epoxy compound having an ester bond in the molecule below the upper limit of the above mass ratio, it is possible to prevent the coating film from undergoing hydrolysis after being left in high temperature and high humidity conditions. It is assumed that it is possible to suppress the deterioration of the film and maintain the physical properties of the coating film after photocuring, such as adhesion.
　また別の好ましい態様は、前記（Ｂ）オキセタン化合物と、前記（Ａ）エポキシ化合物との質量比が、１０：１００～２０：１００の数値範囲にある、硬化性樹脂組成物に関する。
（Ｂ）オキセタン化合物の配合量の比率を上記の範囲に規定することで、塗膜表面と底部の硬化性をバランスよく改善することができる。上記配合量の比率を下限以上とすることで、光硬化後の硬化塗膜のタック性が良好となる。また、上記配合量の比率を上限以下とすることで、硬化塗膜の架橋密度を適度に保ち、柔軟性を維持して、鉛筆硬度や高温高湿条件に放置した後の密着性を向上できる。 Another preferred embodiment relates to a curable resin composition in which the mass ratio of the oxetane compound (B) to the epoxy compound (A) is in the numerical range of 10:100 to 20:100.
(B) By regulating the blending ratio of the oxetane compound within the above range, the curability of the surface and bottom of the coating film can be improved in a well-balanced manner. By setting the ratio of the above-mentioned amount to be equal to or higher than the lower limit, the tackiness of the cured coating film after photocuring will be good. In addition, by keeping the ratio of the above amounts below the upper limit, the crosslinking density of the cured coating film can be maintained at an appropriate level, flexibility can be maintained, and the pencil hardness and adhesion after being left in high temperature and high humidity conditions can be improved. .
　さらにまた別の好ましい態様は、光増感剤としてアルコキシアントラセン誘導体をさらに含む、硬化性樹脂組成物にも関する。 Yet another preferred embodiment also relates to a curable resin composition that further contains an alkoxyanthracene derivative as a photosensitizer.
本発明の硬化性樹脂組成物は、スマートフォン等の黒色遮光剤として好適に用いられることから、より好ましい態様は、硬化後の塗膜の膜厚１０～２０μｍでのＯＤ値が、４以上が好ましく、より好ましくは５以上である。
　ＯＤ値は、例えば、透過濃度計（型番：Ｘ－Ｒｉｔｅ　３６１Ｔ；光源波長４００～８ ００ｎｍ；サカタインクスエンジニアリング社製）を用いて、透過光量を測定し、式ＯＤ 値＝－ｌｏｇ１０（Ｔ／１００）に基づいて算出することができる。 Since the curable resin composition of the present invention is suitably used as a black light shielding agent for smartphones, etc., in a more preferred embodiment, the OD value of the cured coating film at a film thickness of 10 to 20 μm is preferably 4 or more. , more preferably 5 or more.
The OD value is determined by measuring the amount of transmitted light using a transmission densitometer (model number: X-Rite 361T; light source wavelength 400-800 nm; manufactured by Sakata Inx Engineering Co., Ltd.), and using the formula OD value = -log10 (T/100). It can be calculated based on
　上記のとおりの構成を有する本発明の硬化性樹脂組成物は、遮光性が高いだけでなく、塗膜表面の硬化性が良好であり、高温高湿条件下でも安定した密着性を発揮し、かつ硬度も高い硬化塗膜を形成するという優れた利点を有する。さらにまた、本発明の硬化性樹脂組成物は、インクジェット用途に対して好適でもあるため、種々ディスプレイの製造においても製造効率が良好であるという利点をも有する。
　そして、本発明の硬化性樹脂組成物は、上記の特性によって、例えば、ディスプレイの黒色遮光材としての用途に特に適することも期待される。 The curable resin composition of the present invention having the above configuration not only has high light-shielding properties, but also has good curability on the surface of the coating film, and exhibits stable adhesion even under high temperature and high humidity conditions. It also has the excellent advantage of forming a cured coating film with high hardness. Furthermore, since the curable resin composition of the present invention is suitable for inkjet applications, it also has the advantage of good production efficiency in the production of various displays.
The curable resin composition of the present invention is also expected to be particularly suitable for use as a black light-shielding material for displays, for example, due to the above-mentioned properties.
［（Ａ）エポキシ化合物］
　本発明の硬化性樹脂組成物は、形成される硬化物（硬化塗膜）の硬度を高めるために、（Ａ）エポキシ化合物を含有する。特に、本発明の硬化性樹脂組成物は、より高温高湿の過酷な環境に晒された場合でも基材との密着性を高めるため、前記（Ａ）エポキシ化合物として、（ａ）分子内にエステル結合を有する脂環式エポキシ化合物と、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物と、の２種のエポキシ化合物を併用する。 [(A) Epoxy compound]
The curable resin composition of the present invention contains (A) an epoxy compound in order to increase the hardness of the cured product (cured coating film) to be formed. In particular, the curable resin composition of the present invention contains the (a) epoxy compound in the molecule in order to improve adhesion to the base material even when exposed to harsh environments of higher temperature and humidity. Two types of epoxy compounds are used together: an alicyclic epoxy compound having an ester bond, and (b) an alicyclic epoxy compound having no ester bond in the molecule.
　高いＯＤ値を有する硬化性樹脂組成物にエポキシ化合物が用いられる場合には、通常、反応性の高さから、エポキシ化合物のうち脂環式エポキシ化合物が成分の１つとして採用される。とりわけ、硬化性樹脂組成物の使用時における表面硬化性あるいは硬化性の向上という観点から、エステル結合を有する脂環式エポキシ化合物が採用されるのが慣習である。しかしながら、そのようなエステル結合を有する脂環式エポキシ化合物を含む硬化性樹脂組成物であっても、より高温高湿の過酷な環境に晒されるスマートフォン等のディスプレイに対して用いた場合には、基材に対する密着性が十分とならないという不利益がある。 When an epoxy compound is used in a curable resin composition having a high OD value, an alicyclic epoxy compound is usually employed as one of the epoxy compounds due to its high reactivity. In particular, from the viewpoint of improving surface curability or curability when using a curable resin composition, it is customary to employ an alicyclic epoxy compound having an ester bond. However, even with a curable resin composition containing such an alicyclic epoxy compound having an ester bond, when used for displays such as smartphones that are exposed to harsh environments of higher temperature and humidity, There is a disadvantage that adhesion to the base material is not sufficient.
　そこで、本発明は、（Ａ）エポキシ化合物として、（ａ）分子内にエステル結合を有する脂環式エポキシ化合物と、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物と、の２種のエポキシ化合物を併用し、さらにそれだけでなく、これら２種のエポキシ化合物を、５：１００～３０：１００、好ましくは８：１００～２５：１００の数値範囲の質量比で硬化性樹脂組成物中に含むことによって、上記のような不利益の回避が図られたものである。（ａ）分子内にエステル結合を有する脂環式エポキシ化合物の配合量の比率を上記の範囲で規定することで、光硬化後の塗膜についてエステルの加水分解による劣化の影響を抑えつつ、塗膜の柔軟性と硬化性を両立させることで優れた密着性を発揮させることができる。 Therefore, the present invention provides two epoxy compounds: (a) an alicyclic epoxy compound having an ester bond in the molecule; and (b) an alicyclic epoxy compound having no ester bond in the molecule. A curable resin composition is prepared in which two kinds of epoxy compounds are used in combination, and in addition, these two kinds of epoxy compounds are mixed in a mass ratio in a numerical range of 5:100 to 30:100, preferably 8:100 to 25:100. By including it in the above, the above-mentioned disadvantages can be avoided. (a) By specifying the blending ratio of the alicyclic epoxy compound having an ester bond in the molecule within the above range, the coating film can be coated after photocuring while suppressing the effects of deterioration due to ester hydrolysis. Excellent adhesion can be achieved by achieving both flexibility and curability of the film.
　以下、本発明の硬化性樹脂組成物の一成分として用いられる（Ａ）エポキシ化合物に含まれる、（ａ）分子内にエステル結合を有する脂環式エポキシ化合物、および、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物、について説明する。 Hereinafter, (a) an alicyclic epoxy compound having an ester bond in the molecule, which is contained in the epoxy compound (A) used as a component of the curable resin composition of the present invention, and (b) an ester in the molecule. An alicyclic epoxy compound having no bond will be explained.
［（ａ）分子内にエステル結合を有する脂環式エポキシ化合物］
　本発明において、脂環式エポキシ化合物とは、分子内に１個以上の脂肪族環構造を有し、当該脂肪族環中の炭素原子２個と酸素原子がさらなる環となってエポキシ基を形成した構造の化合物をいう。
　そして、（ａ）分子内にエステル結合を有する脂環式エポキシ化合物とは、前記の脂環式エポキシ化合物が、その化学構造中にさらにエステル結合をも有する化合物をいう。 [(a) Alicyclic epoxy compound having an ester bond in the molecule]
In the present invention, an alicyclic epoxy compound has one or more aliphatic ring structures in the molecule, and two carbon atoms and an oxygen atom in the aliphatic ring form an epoxy group. It refers to a compound with the following structure.
And (a) the alicyclic epoxy compound having an ester bond in the molecule refers to a compound in which the above-mentioned alicyclic epoxy compound further has an ester bond in its chemical structure.
　そのような（ａ）分子内にエステル結合を有する脂環式エポキシ化合物として、例えば、下記構造を有するそれぞれの化合物：
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
 　　　　　　　　　
（式中、ｎ１は、１～３０の整数を示す）

Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
 （式中、Ａは、炭素原子数１～８のアルキレン基を表し；ｎ２は、１～３０の整数を示す）

Figure JPOXMLDOC01-appb-C000008
 が好ましく挙げられる。 As such (a) alicyclic epoxy compound having an ester bond in the molecule, for example, each compound having the following structure:
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
(In the formula, n1 represents an integer from 1 to 30)

Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
 (In the formula, A represents an alkylene group having 1 to 8 carbon atoms; n2 represents an integer of 1 to 30)

Figure JPOXMLDOC01-appb-C000008
 are preferred.
　（ａ）分子内にエステル結合を有する脂環式エポキシ化合物として、市販品ももちろん使用することができ、例えば、セロキサイド２０２１Ｐ、またはセロキサイド２０８１（いずれもダイセル社製）が好ましく挙げられる。 (a) As the alicyclic epoxy compound having an ester bond in the molecule, commercially available products can of course be used, and preferred examples include Celloxide 2021P and Celloxide 2081 (both manufactured by Daicel Corporation).
　（ａ）分子内にエステル結合を有する脂環式エポキシ化合物は、１種単独または２種以上組み合わせて用いられてももちろんよい。 Of course, (a) the alicyclic epoxy compound having an ester bond in the molecule may be used alone or in combination of two or more.
［（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物］
　本発明において、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物とは、上記（ａ）分子内にエステル結合を有する脂環式エポキシ化合物の項において説明された脂環式エポキシ化合物が、その分子内にエステル結合を有するものではない化合物、例えばエステル結合の代わりにエーテル結合を有する脂環式エポキシ化合物などをいう。
　（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物としては、例えば下記構造を有する化合物：
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
 が挙げられる。 [(b) Alicyclic epoxy compound having no ester bond in the molecule]
In the present invention, (b) an alicyclic epoxy compound that does not have an ester bond in the molecule refers to the alicyclic epoxy compound described in the section of (a) the alicyclic epoxy compound that has an ester bond in the molecule above. However, it refers to a compound that does not have an ester bond in its molecule, such as an alicyclic epoxy compound that has an ether bond instead of an ester bond.
(b) Examples of alicyclic epoxy compounds that do not have an ester bond in the molecule include compounds having the following structure:
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
 can be mentioned.
　（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物としては市販品ももちろん使用することができ、例えば、リモネンジオキシド（ＬＤＯ）（ＳＹＭＲＩＳＥ社製）、ＴＨＩ－ＤＥ、ＤＥ－１０２およびＤＥ－１０３（ＪＸＴＧエネルギー社製）、Ｘ－４０－２６７８およびＸ－４０－２６６９（信越化学工業社製）、ＥＨＰＥ－３１５０およびＣＥＬＬＯＸＩＤＥ２０００（ダイセル社製）、ならびに、ＫＲ－４７０（信越化学社製）などが好ましく挙げられる。 (b) As the alicyclic epoxy compound having no ester bond in the molecule, commercially available products can of course be used, such as limonene dioxide (LDO) (manufactured by SYMRISE), THI-DE, DE-102 and DE-103 (made by JXTG Energy), ) etc. are preferably mentioned.
　また、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物のうち、本発明においてより好ましくは、２官能のエポキシ基を有するものである。
　このような（ｂ）分子内にエステル結合を有しない脂環式２官能エポキシ化合物は、分子中に、下記構造式：
Figure JPOXMLDOC01-appb-C000013
 で表されるエチレンオキシド基、および／または、下記構造式：
Figure JPOXMLDOC01-appb-C000014
 で表されるシクロヘキセンオキシド基を、合計２個有する化合物である。
　市販品としては例えば、ＴＨＩ－ＤＥ、ＤＥ－１０２およびＤＥ－１０３（ＪＸＴＧエネルギー社製）、Ｘ－４０－２６７８およびＸ－４０－２６６９（信越化学工業社製）などが挙げられる。 Further, among the alicyclic epoxy compounds (b) having no ester bond in the molecule, those having a difunctional epoxy group are more preferred in the present invention.
Such (b) alicyclic bifunctional epoxy compound having no ester bond in the molecule has the following structural formula in the molecule:
Figure JPOXMLDOC01-appb-C000013
 Ethylene oxide group represented by and/or the following structural formula:
Figure JPOXMLDOC01-appb-C000014
 It is a compound having a total of two cyclohexene oxide groups represented by
Commercially available products include, for example, THI-DE, DE-102 and DE-103 (manufactured by JXTG Energy Corporation), and X-40-2678 and X-40-2669 (manufactured by Shin-Etsu Chemical Co., Ltd.).
　（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物は、１種単独または２種以上組み合わせて用いられてももちろんよい。 (b) The alicyclic epoxy compound having no ester bond in the molecule may be used alone or in combination of two or more.
　本発明の硬化性樹脂組成物中の（ａ）分子内にエステル結合を有する脂環式エポキシ化合物の全含有量は、硬化性およびタック性の観点から、（Ａ）エポキシ化合物と（Ｂ）オキセタン化合物の合計１００質量部に対して、３～６０質量部が好ましく、３～３０質量部がより好ましい。
　また（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物の全含有量は、基材との密着性の観点から、（Ａ）エポキシ化合物と（Ｂ）オキセタン化合物の合計１００質量部に対して、３０～９０質量部が好ましく、４０～８０質量部がより好ましい。
　但し、これら（ａ）および（ｂ）の２種の脂環式エポキシ化合物のそれぞれの含有量は互いに、既に上記したとおりの特定の数値範囲内の比率に調整されることを要する。 The total content of (a) the alicyclic epoxy compound having an ester bond in the molecule in the curable resin composition of the present invention is determined from the viewpoints of curability and tackiness. It is preferably 3 to 60 parts by weight, more preferably 3 to 30 parts by weight, based on a total of 100 parts by weight of the compound.
In addition, the total content of (b) alicyclic epoxy compound that does not have an ester bond in the molecule is 100 parts by mass in total of (A) epoxy compound and (B) oxetane compound from the viewpoint of adhesion to the base material. On the other hand, it is preferably 30 to 90 parts by weight, more preferably 40 to 80 parts by weight.
However, the respective contents of these two types of alicyclic epoxy compounds (a) and (b) need to be adjusted to a ratio within the specific numerical range as already described above.
［その他のエポキシ化合物］
　本発明の硬化性樹脂組成物は、上記（ａ）分子内にエステル結合を有する脂環式エポキシ化合物および（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物に加えて、本発明の硬化性樹脂組成物の特性をさらに向上させる目的で、または新たな特性を付与させる目的で、（Ａ）エポキシ化合物として、（ａ）および（ｂ）以外のエポキシ化合物、例えば、非脂環式エポキシ化合物などを、その他のエポキシ化合物としてさらに含有することも勿論可能である。
　本発明で用いられ得る当該その他のエポキシ化合物は慣用のもので十分であるため、ここではその全てを列挙することはないが、敢えて好ましいものとして、例えば、デナコールＥＸ－２１２およびデナコールＥＸ－１２１（いずれもデナコール社製）、ならびにＫＢＭ－４０３（信越シリコーン社製）等が挙げられる。
そのようなその他のエポキシ化合物を含有する場合の全含有量は、（Ａ）エポキシ化合物（（ａ）および（ｂ）のエポキシ化合物とその他のエポキシ化合物も含む）と（Ｂ）オキセタン化合物の合計１００質量部に対して、１３０質量部が好ましく、３～２０質量部がより好ましい。 [Other epoxy compounds]
The curable resin composition of the present invention comprises (a) an alicyclic epoxy compound having an ester bond in the molecule and (b) an alicyclic epoxy compound having no ester bond in the molecule, as well as For the purpose of further improving the properties of the curable resin composition or imparting new properties, as the epoxy compound (A), epoxy compounds other than (a) and (b), such as non-alicyclic epoxy Of course, it is also possible to further contain compounds as other epoxy compounds.
Since the other epoxy compounds that can be used in the present invention are commonly used, they are not all listed here, but preferable ones include Denacol EX-212 and Denacol EX-121 ( (all manufactured by Denacol), and KBM-403 (manufactured by Shin-Etsu Silicone).
When such other epoxy compounds are contained, the total content is the total of (A) epoxy compounds (including the epoxy compounds of (a) and (b) and other epoxy compounds) and (B) oxetane compounds (100 It is preferably 130 parts by weight, more preferably 3 to 20 parts by weight.
［（Ｂ）オキセタン化合物］
　本発明の硬化性樹脂組成物においては、硬化物の硬度の向上の観点から、熱硬化性樹脂として（Ｂ）オキセタン化合物が含有される。但し、本発明においては、当該（Ｂ）オキセタン化合物の含有量は、上記の（Ａ）エポキシ化合物の全量、即ち、（ａ）分子内にエステル結合を有する脂環式エポキシ化合物、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物およびその他のエポキシ化合物の総量に対して、特定の数値範囲の質量比となるように調整される。具体的には、（Ｂ）オキセタン化合物の含有量は、当該（Ｂ）オキセタン化合物と、（Ａ）エポキシ化合物との質量比が、２：１００～４０：１００の数値範囲となるように、好ましくは、１０：１００～２０：１００の数値範囲となるように、調整される。 [(B) Oxetane compound]
In the curable resin composition of the present invention, (B) an oxetane compound is contained as a thermosetting resin from the viewpoint of improving the hardness of the cured product. However, in the present invention, the content of the (B) oxetane compound is the total amount of the above (A) epoxy compound, that is, (a) an alicyclic epoxy compound having an ester bond in the molecule; The mass ratio is adjusted to be within a specific numerical range with respect to the total amount of the alicyclic epoxy compound and other epoxy compounds that do not have an ester bond therein. Specifically, the content of the (B) oxetane compound is preferably such that the mass ratio of the (B) oxetane compound to the (A) epoxy compound is in the numerical range of 2:100 to 40:100. is adjusted to have a numerical value range of 10:100 to 20:100.
　かような（Ｂ）オキセタン化合物としては、単官能のものに限らず、多官能のものも使用され得る。
　単官能の（Ｂ）オキセタン化合物としては、例えば、３－メチルオキセタン、３－エチルオキセタン、３－ヒドロキシメチルオキセタン、３－メチル－３－ヒドロキシメチルオキセタン、３－エチル－３－ヒドロキシメチルオキセタン等が挙げられる。 The oxetane compound (B) is not limited to monofunctional ones, but polyfunctional ones can also be used.
Examples of the monofunctional oxetane compound (B) include 3-methyloxetane, 3-ethyloxetane, 3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, and 3-ethyl-3-hydroxymethyloxetane. Can be mentioned.
　また、多官能の（Ｂ）オキセタン化合物としては、ビス［（３－メチル－３－オキセタニルメトキシ）メチル］エーテル、ビス［（３－エチル－３－オキセタニルメトキシ）メチル］エーテル、１，４－ビス［（３－メチル－３－オキセタニルメトキシ）メチル］ベンゼン、１，４－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］ベンゼン、（３－メチル－３－オキセタニル）メチルアクリレート、（３－エチル－３－オキセタニル）メチルアクリレート、（３－メチル－３－オキセタニル）メチルメタクリレート、（３－エチル－３－オキセタニル）メチルメタクリレートやそれらのオリゴマーまたは共重合体等の多官能オキセタン類の他、オキセタンアルコールとノボラック樹脂、ポリ（ｐ－ヒドロキシスチレン）、カルド型ビスフェノール類、カリックスアレーン類、カリックスレゾルシンアレーン類、またはシルセスキオキサンなどの水酸基を有する樹脂とのエーテル化物などが挙げられる。その他、オキセタン環を有する不飽和モノマーとアルキル（メタ）アクリレートとの共重合体なども挙げられる。 In addition, as the polyfunctional oxetane compound (B), bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3- Oxetane Examples include etherification products of alcohols with novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, or resins having hydroxyl groups such as silsesquioxane. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth)acrylates.
　（Ｂ）オキセタン化合物として市販品を用いることも勿論可能である。例えば、ＯＸＴ－１０１、ＯＸＴ－１２１、ＯＸＴ－２１２およびＯＸＴ－２２１（東亜合成社製）が好ましい。 It is of course possible to use a commercially available product as the oxetane compound (B). For example, OXT-101, OXT-121, OXT-212 and OXT-221 (manufactured by Toagosei Co., Ltd.) are preferred.
　本発明の硬化性樹脂組成物は、上記の（Ｂ）オキセタン化合物を１種単独または２種以上含有しても勿論良い。 Of course, the curable resin composition of the present invention may contain one or more of the above (B) oxetane compounds.
かかる（Ｂ）オキセタン化合物の含有量としては、硬化物の硬度の観点から、（Ａ）エポキシ化合物と（Ｂ）オキセタン化合物の合計１００質量部に対し、３～４０質量部が好ましく、８～３０質量部がより好ましい。
　但し、（Ｂ）オキセタン化合物の含有量は、含有する（Ａ）エポキシ化合物の質量との質量比が上記のとおりの特定の数値範囲内となるよう調整されることを要する。
　（Ａ）エポキシ化合物及び（Ｂ）オキセタン化合物の合計の配合量は、本発明の硬化性樹脂組成物の質量を基準として、２５～９５質量％が好ましく、３５～９０質量%がより好ましい。 The content of the oxetane compound (B) is preferably 3 to 40 parts by mass, and 8 to 30 parts by mass, based on the total of 100 parts by mass of the epoxy compound (A) and the oxetane compound (B), from the viewpoint of the hardness of the cured product. Parts by mass are more preferred.
However, the content of the (B) oxetane compound needs to be adjusted so that the mass ratio to the mass of the contained (A) epoxy compound falls within the specific numerical range as described above.
The total amount of the epoxy compound (A) and the oxetane compound (B) is preferably 25 to 95% by mass, more preferably 35 to 90% by mass, based on the mass of the curable resin composition of the present invention.
［（Ｃ）光酸発生剤］
  本発明の硬化性樹脂組成物においては、紫外線照射によりカチオン重合を開始させる
物質を発生させることが可能な化合物として、（Ｃ）光酸発生剤が含有される。
（Ｃ）光酸発生剤としては、例えば、ジアゾニウム塩、ヨードニウム塩、ブロモニウム塩、クロロニウム塩、スルホニウム塩、セレノニウム塩、ピリリウム塩、チアピリリウム塩、ピリジニウム塩等のオニウム塩；トリス（トリハロメチル）－ｓ－トリアジンおよびその誘導体等のハロゲン化化合物；スルホン酸の２－ニトロベンジルエステル；イミノスルホナート；１－オキソ－２－ジアゾナフトキノン－４－スルホナート誘導体；Ｎ－ヒドロキシイミドスルホナート；トリ（メタンスルホニルオキシ）ベンゼン誘導体；ビススルホニルジアゾメタン類；スルホニルカルボニルアルカン類；スルホニルカルボニルジアゾメタン類；ジスルホン化合物等が挙げられる。
  これらの（Ｃ）光酸発生剤は単独で、または２種以上を組み合わせて用いることができる。 [(C) Photoacid generator]
The curable resin composition of the present invention contains (C) a photoacid generator as a compound capable of generating a substance that initiates cationic polymerization upon irradiation with ultraviolet rays.
(C) Photoacid generators include, for example, onium salts such as diazonium salts, iodonium salts, bromonium salts, chloronium salts, sulfonium salts, selenonium salts, pyrylium salts, thiapyrylium salts, and pyridinium salts; tris(trihalomethyl)-s -halogenated compounds such as triazines and their derivatives; 2-nitrobenzyl esters of sulfonic acids; iminosulfonates; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivatives; N-hydroxyimidosulfonates; tri(methanesulfonyloxy) ) benzene derivatives; bissulfonyldiazomethanes; sulfonylcarbonylalkanes; sulfonylcarbonyldiazomethanes; disulfone compounds and the like.
These (C) photoacid generators can be used alone or in combination of two or more.
　（Ｃ）光酸発生剤としては市販品を用いることもでき、例えば、ＣＰＩ－１００Ｐ、ＣＰＩ－２００Ｋ、ＣＰＩ－１０１Ａ（以上、サンアプロ社製）、サイラキュア光硬化開始剤ＵＶＩ－６９９０、サイラキュア光硬化開始剤ＵＶＩ－６９９２、サイラキュア光硬化開始剤ＵＶＩ－６９７６（以上、ダウ・ケミカル日本社製）、アデカオプトマーＳＰ－１５０、アデカオプトマーＳＰ－１５２、アデカオプトマーＳＰ－１７０、アデカオプトマーＳＰ－１７２（以上、旭電化工業社製）、ＣＩ－５１０２、ＣＩ－２８５５（以上、日本曹達社製）、サンエイドＳＩ－６０Ｌ、サンエイドＳＩ－８０Ｌ、サンエイドＳＩ－１００Ｌ、サンエイドＳＩ－１１０Ｌ、サンエイドＳＩ－１８０Ｌ、サンエイドＳＩ－１１０、サンエイドＳＩ－１４５、サンエイドＳＩ－１５０、サンエイドＳＩ－１６０、サンエイドＳＩ－１８０（以上、三新化学工業社製）、エサキュア１０６４、エサキュア１１８７（以上、ランベルティ社製）、オムニキャット４３２、オムニキャット４４０、オムニキャット４４５、オムニキャット５５０、オムニキャット６５０、オムニキャットＢＬ－５５０、オムニキャット２５０（アイジーエム レジン社製）、ロードシル フォトイニシエーター２０７４（ＲＨＯＤＯＲＳＩＬ ＰＨＯＴＯＩＮＩＴＩＡＴＯＲ ２０７４（ローディア・ジャパン社製）、ＷＰＩ－１１３、ＷＰＩ－１１６、ＷＰＩ－１６９、ＷＰＩ－１７０（和光純薬工業社製）等が挙げられる。 (C) Commercially available products can be used as the photoacid generator, such as CPI-100P, CPI-200K, CPI-101A (manufactured by Sun-Apro), Cylacure photocuring initiator UVI-6990, Cylacure photocuring Initiator UVI-6992, Silacure photocuring initiator UVI-6976 (manufactured by Dow Chemical Japan Co., Ltd.), ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-152, ADEKA OPTOMER SP-170, ADEKA OPTOMER SP -172 (manufactured by Asahi Denka Kogyo Co., Ltd.), CI-5102, CI-2855 (manufactured by Nippon Soda Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, Sun-Aid SI -180L, SunAid SI-110, SunAid SI-145, SunAid SI-150, SunAid SI-160, SunAid SI-180 (all manufactured by Sanshin Kagaku Kogyo Co., Ltd.), Esacure 1064, Esacure 1187 (all manufactured by Lamberti) ), Omnicat 432, Omnicat 440, Omnicat 445, Omnicat 550, Omnicat 650, Omnicat BL-550, Omnicat 250 (manufactured by IGM Resin), RHODORSIL PHOTOINITIATOR 2074 (Rhodia・WPI-113, WPI-116, WPI-169, and WPI-170 (manufactured by Wako Pure Chemical Industries, Ltd.).
  これらの中では、ＣＰＩ－１００Ｐ、ＣＰＩ－１０１Ａ、ＣＰＩ－２００Ｋ、ＣＰＩ－２１０Ｓ、あるいは芳香族ヨードニウム塩であるオムニキャット２５０、ＷＰＩ－１１３、ＷＰＩ－１１６、ＷＰＩ－１６９およびＷＰＩ－１７０が好ましい。 Among these, CPI-100P, CPI-101A, CPI-200K, CPI-210S, or aromatic iodonium salts Omnicat 250, WPI-113, WPI-116, WPI-169 and WPI-170 are preferred.
硬化性樹脂組成物における（Ｃ）光酸発生剤の含有量は、（Ａ）エポキシ化合物と（Ｂ）オキセタン化合物の合計１００質量部に対して、５～３０質量部が好ましく、より好ましくは、７～１５質量部である。 The content of the photoacid generator (C) in the curable resin composition is preferably 5 to 30 parts by mass, and more preferably, It is 7 to 15 parts by mass.
［（Ｄ）黒色着色剤］
　本発明の硬化性樹脂組成物は、通常、黒色遮光用として用いられる観点から、（Ｄ）黒色着色剤、特に黒色顔料を含有するのが好ましい。典型的には、カーボンブラックなどの黒色顔料が好ましく用いられるが、用途の観点から大きく外れない範囲内において、黒色染料、その他の色彩を有する着色剤が用いられてもよいし、カーボンブラックに加えてさらに含有されても勿論よい。 [(D) Black colorant]
The curable resin composition of the present invention preferably contains (D) a black colorant, particularly a black pigment, from the viewpoint that it is usually used for black light shielding. Typically, black pigments such as carbon black are preferably used, but black dyes and other coloring agents may also be used within a range that does not deviate greatly from the viewpoint of the intended use, or in addition to carbon black. Of course, it may be further contained.
　黒色顔料としては、例えば、カーボンブラックの他、四三酸化鉄（Ｆｅ３Ｏ４）、黒酸化チタン、銅マンガンブラック、銅クロムブラックおよびコバルトブラック等の無機顔料、並びにシアニンブラックおよびアニリンブラック等の有機顔料が挙げられる。 Examples of black pigments include, in addition to carbon black, inorganic pigments such as triiron tetroxide (Fe 3 O 4 ), black titanium oxide, copper manganese black, copper chrome black, and cobalt black, and cyanine black and aniline black. Examples include organic pigments.
　また、その他の色彩を有する着色剤としては、公知慣用の赤、青、緑、黄色の顔料または染料が挙げられる。 In addition, examples of colorants having other colors include known and commonly used red, blue, green, and yellow pigments or dyes.
本発明の硬化性樹脂組成物における（Ｄ）黒色着色剤の含有量は、形成する硬化物の用途を考慮して調整されるが、塗膜の硬化性と密着性のバランスの観点から、（Ａ）エポキシ化合物と（Ｂ）オキセタン化合物の合計１００質量部に対して５質量部以上含まれることが好ましく、より好ましくは、５質量部以上１５質量部以下である。 The content of the black colorant (D) in the curable resin composition of the present invention is adjusted in consideration of the use of the cured product to be formed, but from the viewpoint of the balance between curability and adhesion of the coating film, ( The content is preferably 5 parts by mass or more, more preferably 5 parts by mass or more and 15 parts by mass or less, based on a total of 100 parts by mass of A) the epoxy compound and (B) the oxetane compound.
［光増感剤］
　本発明の硬化性樹脂組成物は、光感度をより高めるために、光増感剤をさらに含有するのが好ましい。
　当該光増感剤は、波長３５０ｎｍ～４５０ｎｍの光によって励起状態となる化合物であることが好ましい。例として、ピレン、ペリレン、トリフェニレン、アントラセン等の多核芳香族類；フルオレッセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガル等のキサンテン類；キサントン、チオキサントン、ジメチルチオキサントン、ジエチルチオキサントン等のキサントン類；チアカルボシアニン、オキサカルボシアニン等のシアニン類；メロシアニン、カルボメロシアニン等のメロシアニン類；ローダシアニン類；オキソノール類；チオニン、メチレンブルー、トルイジンブルー等のチアジン類；アクリジンオレンジ、クロロフラビン、アクリフラビン等のアクリジン類；アクリドン、１０－ブチル－２－クロロアクリドン等のアクリドン類；アントラキノン類；スクアリウム類；スチリル類；ベーススチリル類；７－ジエチルアミノ４－メチルクマリン等のクマリン類が挙げられる。これらの中で、アントラセン化合物、特にアルコキシアントラセン誘導体が好ましい。
　これら光増感剤は、それらの２種以上を組み合わせて用いてももちろん構わない。 [Photosensitizer]
The curable resin composition of the present invention preferably further contains a photosensitizer in order to further increase photosensitivity.
The photosensitizer is preferably a compound that becomes excited by light with a wavelength of 350 nm to 450 nm. Examples include polynuclear aromatics such as pyrene, perylene, triphenylene, and anthracene; xanthenes such as fluorescein, eosin, erythrosin, rhodamine B, and rose bengal; xanthone such as xanthone, thioxanthone, dimethylthioxanthone, and diethylthioxanthone; Cyanines such as carbocyanine and oxacarbocyanine; merocyanines such as merocyanine and carbomerocyanine; rhodacyanines; oxonols; thiazines such as thionine, methylene blue and toluidine blue; acridines such as acridine orange, chloroflavin and acriflavin ; acridones such as acridone and 10-butyl-2-chloroacridone; anthraquinones; squaliums; styryls; basestyryls; and coumarins such as 7-diethylamino 4-methylcoumarin. Among these, anthracene compounds, particularly alkoxyanthracene derivatives, are preferred.
Of course, two or more of these photosensitizers may be used in combination.
　光増感剤としては市販品を用いることも可能である。そのような例としては、アントラキュアー（登録商標）ＵＶＳ－１１０１（ジエトキシアントラセン；川崎化成工業株式会社製）、アントラキュアー（登録商標）ＵＶＳ－１２２１（ジプロポキシアントラセン；川崎化成工業株式会社製）、アントラキュアー（登録商標）ＵＶＳ－１３３１（ジブトキシアントラセン；川崎化成工業株式会社製）等のアルコキシアントラセン誘導体が好ましく挙げられる。 It is also possible to use commercially available products as the photosensitizer. Such examples include Anthracure (registered trademark) UVS-1101 (diethoxyanthracene; manufactured by Kawasaki Chemical Industries, Ltd.), Anthracure (registered trademark) UVS-1221 (dipropoxyanthracene; manufactured by Kawasaki Chemical Industries, Ltd.). Preferred examples include alkoxyanthracene derivatives such as Anthracure (registered trademark) UVS-1331 (dibutoxyanthracene; manufactured by Kawasaki Chemical Industries, Ltd.).
　光増感剤の含有量は、上記の光酸発生剤１質量部に対し０．１～２．０質量部であり、好ましくは、０．２～１．０質量部％である。 The content of the photosensitizer is 0.1 to 2.0 parts by mass, preferably 0.2 to 1.0 parts by mass, per 1 part by mass of the photoacid generator.
［その他の成分］
　また、本発明の硬化性樹脂組成物は、その特性を損なわない範囲において、例えば、溶剤、反応性希釈剤、分散剤、増粘剤、界面活性剤、酸化防止剤、可塑剤、難燃剤、帯電防止剤、レベリング剤、消泡剤および抗菌剤等のその他の成分をさらに含有していてもよい。本発明の硬化性樹脂組成物の粘度を低下させることができる反応性希釈剤としては、光反応性希釈剤が好ましい。光反応性希釈剤としては、（メタ）アクリレート類、ビニルエーテル類、エチレン誘導体、スチレン、クロロメチルスチレン、α－メチルスチレン、無水マレイン酸、ジシクロペンタジエン、Ｎ－ビニルピロリドン、Ｎ－ビニルホルムアミド、キシリレンジオキセタン、オキセタンアルコール、３－エチル－３－（フェノキシメチル）オキセタン、レゾルシノールジグリシジルエーテル等の不飽和二重結合やオキセタニル基、エポキシ基を有する化合物が挙げられる。これらの中でも（メタ）アクリレート類が好ましい。 [Other ingredients]
In addition, the curable resin composition of the present invention may contain, for example, a solvent, a reactive diluent, a dispersant, a thickener, a surfactant, an antioxidant, a plasticizer, a flame retardant, within a range that does not impair its properties. Other components such as antistatic agents, leveling agents, antifoaming agents, and antibacterial agents may also be contained. As the reactive diluent capable of reducing the viscosity of the curable resin composition of the present invention, a photoreactive diluent is preferable. Examples of photoreactive diluents include (meth)acrylates, vinyl ethers, ethylene derivatives, styrene, chloromethylstyrene, α-methylstyrene, maleic anhydride, dicyclopentadiene, N-vinylpyrrolidone, N-vinylformamide, and xylene. Examples include compounds having an unsaturated double bond, an oxetanyl group, and an epoxy group, such as dioxetane, oxetane alcohol, 3-ethyl-3-(phenoxymethyl)oxetane, and resorcinol diglycidyl ether. Among these, (meth)acrylates are preferred.
［硬化物およびその製造方法］
　本発明の硬化性樹脂組成物は、インクジェット法によって基板の目的箇所に適用され、そして硬化させることによって硬化物を形成する。
　インクジェット印刷方式として好適であるのはオンデマンド方式のピエゾ方式であるが、特に限定されるわけではない。好適な波長としては紫外領域の３６５ｎｍ、３８５ｎｍ、３９５ｎｍ、４０５ｎｍなど挙げられるが、特に限定されるわけではない。
　硬化は、適用した組成物に対する活性エネルギー線の照射によって行われる。
　活性エネルギー線の照射光源としては、ＬＥＤ、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプなどが適当である。その他、電子線、α線、β線、γ線、Ｘ線、中性子線なども利用可能である。なお、照射光源は１つまたは２つ以上で、２つ以上の場合は異なる波長の光源を組み合わせて使用することももちろん可能である。 [Cured product and its manufacturing method]
The curable resin composition of the present invention is applied to a target location on a substrate by an inkjet method, and is cured to form a cured product.
A suitable inkjet printing method is an on-demand piezo method, but the method is not particularly limited. Suitable wavelengths include 365 nm, 385 nm, 395 nm, 405 nm, etc. in the ultraviolet region, but are not particularly limited.
Curing is performed by irradiating the applied composition with active energy radiation.
Suitable light sources for irradiating active energy rays include LEDs, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, and the like. In addition, electron beams, α rays, β rays, γ rays, X rays, neutron beams, etc. can also be used. Note that the number of irradiation light sources is one or two or more, and in the case of two or more, it is of course possible to use a combination of light sources of different wavelengths.
  また、活性エネルギー線による露光量は、通常、１０～１００００ｍＪ／ｃｍ２、好ましくは２０～２０００ｍＪ／ｃｍ２、より好ましくは１００～２０００ｍＪ／ｃｍ２の範囲内である。 The amount of exposure to active energy rays is usually in the range of 10 to 10,000 mJ/cm 2 , preferably 20 to 2,000 mJ/cm 2 , and more preferably 100 to 2,000 mJ/cm 2 .
　以下、実施例および比較例を示して本発明について具体的に説明するが、本発明が以下の実施例に限定されるものでないことは言うまでもない。
　なお、他に特に但書が無い限り、示される「部」および「％」は質量に基づくものとする。 EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to the Examples below.
Note that unless otherwise specified, "parts" and "%" shown are based on mass.
　下記表１に記載の配合量に従って、各成分をそれぞれ配合し、攪拌機にて予備混合して、実施例１～１０および比較例１～４の硬化性樹脂組成物を調製した。
　なお、表中の配合量の数値は、特に断りがない限り、質量部を示す。 According to the amounts listed in Table 1 below, each component was blended and premixed using a stirrer to prepare curable resin compositions for Examples 1 to 10 and Comparative Examples 1 to 4.
In addition, the numerical values of the blending amounts in the table indicate parts by mass unless otherwise specified.
Figure JPOXMLDOC01-appb-T000015
 ※表１中の各番号に対応する成分は下記のとおりである。
１）（ａ）分子内にエステル結合を有する脂環式エポキシ化合物：セロキサイド２０２１Ｐ（ダイセル社製）化学名：３，４－エポキシシクロヘキシルメチル（３，４－エポキシ）シクロヘキサンカルボキシレート
２）（ａ）分子内にエステル結合を有する脂環式エポキシ化合物：セロキサイド２０８１（ダイセル社製）化学名：ε－カプロラクトン変性３，４－エポキシシクロヘキシルメチル３'，４'－エポキシシクロヘキサンカルボキレート
３）（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物：ＬＤＯ（ＳＹＭＲＩＳＥ社製）化学名：リモネンジオキサイド
４）（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物：ＴＨＩ－ＤＥ（ＪＸＴＧエネルギー社製）化学名：テトラヒドロインデンジエポキシド
５）その他のエポキシ化合物：デナコールＥＸ－２１２（ナガセケムテックス社製）化学名：１，６－ヘキサンジオールジグリシジルエーテル
６）その他のエポキシ化合物：デナコールＥＸ－１２１（ナガセケムテックス社製）化学名：２－エチルヘキシルグリシジルエーテル
７）その他のエポキシ化合物：ＫＢＭ－４０３（信越化学社製）有機官能基としてエポキシ基を持つシランカップリング剤　化学名：３－グリシドキシプロピルトリメトキシシラン
８）（Ｂ）単官能オキセタン化合物：ＯＸＴ－２１２（東亞合成社製）化学名：２－エチルヘキシルオキセタン
９）（Ｂ）二官能オキセタン化合物：ＯＸＴ－２２１（東亞合成社製）化学名：３－エチル－３｛［（３－エチルオキセタン－３－イル）メトキシ］メチル｝オキセタン
１０）光増感剤：アントラキュアー　ＵＶＳ－１３３１（川崎化成工業社製）
化学名：９，１０－ジブトキシアントラセン
１１）（Ｃ）光酸発生剤：ＣＰＩ－１００Ｐ（固形分５０％）（サンアプロ社製）
化学名：ジフェニル［４－（フェニルスルファニル）フェニル］スルホニウム＝ヘキサフルオロ－λ５－ホスファヌイド
１２）（Ｃ）光酸発生剤：オムニキャット２５０（アイジーエム レジン社製）
化学名：４－イソブチルフェニル(４－メチルフェニル)ヨードニウム・ヘキサフルオロホスファート（固形分７５%）
１３）（Ｄ）黒色着色剤：Ｐｉｇｍｅｎｔ　ｂｌａｃｋ ７（カーボンブラック）
Figure JPOXMLDOC01-appb-T000015
 *The components corresponding to each number in Table 1 are as follows.
1) (a) Alicyclic epoxy compound having an ester bond in the molecule: Celloxide 2021P (manufactured by Daicel) Chemical name: 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate 2) (a) Alicyclic epoxy compound having an ester bond in the molecule: Celloxide 2081 (manufactured by Daicel) Chemical name: ε-caprolactone modified 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate 3) (b) molecule Alicyclic epoxy compound that does not have an ester bond in the molecule: LDO (manufactured by SYMRISE) Chemical name: Limonene dioxide 4) (b) Alicyclic epoxy compound that does not have an ester bond in the molecule: THI-DE (JXTG Energy Chemical name: Tetrahydroindene diepoxide 5) Other epoxy compounds: Denacol EX-212 (manufactured by Nagase ChemteX) Chemical name: 1,6-hexanediol diglycidyl ether 6) Other epoxy compounds: Denacol EX- 121 (manufactured by Nagase ChemteX) Chemical name: 2-ethylhexyl glycidyl ether 7) Other epoxy compounds: KBM-403 (manufactured by Shin-Etsu Chemical) Silane coupling agent with an epoxy group as an organic functional group Chemical name: 3-Glycidyl ether Sidoxypropyltrimethoxysilane 8) (B) Monofunctional oxetane compound: OXT-212 (manufactured by Toagosei Co., Ltd.) Chemical name: 2-ethylhexyloxetane 9) (B) Bifunctional oxetane compound: OXT-221 (manufactured by Toagosei Co., Ltd.) ) Chemical name: 3-ethyl-3 {[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane 10) Photosensitizer: Anthracure UVS-1331 (manufactured by Kawasaki Chemical Industries, Ltd.)
Chemical name: 9,10-dibutoxyanthracene 11) (C) Photoacid generator: CPI-100P (solid content 50%) (manufactured by San-Apro)
Chemical name: Diphenyl[4-(phenylsulfanyl)phenyl]sulfonium=hexafluoro-λ5-phosphanoid 12) (C) Photoacid generator: Omnicat 250 (manufactured by IGM Resin)
Chemical name: 4-isobutylphenyl(4-methylphenyl)iodonium hexafluorophosphate (solid content 75%)
13) (D) Black colorant: Pigment black 7 (carbon black)
　得られた実施例１～１０および比較例１～４の硬化性樹脂組成物から、膜厚５μｍの硬化物（硬化塗膜）をそれぞれ得、下記のとおり、当該硬化物について、クロスカット、鉛筆硬度およびＵＶ硬化後の指触乾燥性を測定した。
実施例１～１０および比較例１～４の硬化性樹脂組成物の粘度は、インキ温度５０℃、１００ｒｐｍに おける粘度をコーンプレート型粘度計（東機産業社製ＴＶＥ－３３Ｈ）にて測定したところ、いずれも５～２０ｍＰａ・ｓの範囲であった。 From the obtained curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4, cured products (cured coating films) with a film thickness of 5 μm were obtained, and the cured products were subjected to cross-cutting, pencil cutting, etc. as described below. Hardness and dryness to touch after UV curing were measured.
The viscosity of the curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 was determined by measuring the viscosity at an ink temperature of 50°C and 100 rpm using a cone plate viscometer (TVE-33H manufactured by Toki Sangyo Co., Ltd.). However, in all cases, the pressure was in the range of 5 to 20 mPa·s.
［試験基板の作製］
　下記条件にて、インクジェットプリンタを用いて、実施例１～１０および比較例１～４の硬化性樹脂組成物を基材に描画し、次いでＵＶ硬化させて、試験基板をそれぞれ作製した。なお、基材として、ガラス基板（１１０ｍｍ×１６０ｍｍ、厚み１ｍｍ）を使用した。
・インクジェットプリンタによる描画条件
　硬化後の膜厚：５μｍ
　装置：ピエゾ方式インクジェットプリンタ（富士フィルム社製　マテリアルプリンタＤＭＰ－２８３１を使用（ヘッド温度５０℃））
・ＵＶ硬化条件
　ＬＥＤ－ＵＶランプ（Ｐｈｏｓｅｏｎ ＴＥＣＨＮＯＬＯＧＹ社製 ＦｉｒｅＥｄｇｅ ＦＥ４００）
　露光量：１５００ｍＪ／ｃｍ２
　波長：３６５ｎｍ [Preparation of test board]
The curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were drawn on a substrate using an inkjet printer under the following conditions, and then UV cured to prepare test substrates. Note that a glass substrate (110 mm x 160 mm, thickness 1 mm) was used as the base material.
・Drawing conditions with inkjet printer Film thickness after curing: 5μm
Equipment: Piezo inkjet printer (uses Fuji Film Material Printer DMP-2831 (head temperature 50°C))
・UV curing conditions LED-UV lamp (FireEdge FE400 manufactured by Phoseon TECHNOLOGY)
Exposure amount: 1500mJ/ cm2
Wavelength: 365nm
［クロスカット］
　ＪＩＳ　Ｋ　５６００－５－６　１９９９に準拠して、［試験基板の作製］で得られた実施例１～１０および比較例１～４の硬化性樹脂組成物の各試験基板上の硬化塗膜を、１ｍｍ間隔用クロスカットガイドを用いてカットして、縦横それぞれ幅１ｍｍのマス目を２５個（５×５）作製し、透明付着テープ（幅２５±１ｍｍ）を硬化塗膜のマス目にカットした部分に貼り、硬化塗膜が透けて見えるようにしっかり指でテープをこすり、付着して５分以内に６０度に近い角度で、０．５～１．０秒で確実に引き離し（テープピーリング）、マス目の状態を調べた。
　当該クロスカットは、硬化塗膜作製後、２３℃湿度５０％ＲＨに３ｈ放置後（初期密着）と、温度８５℃かつ相対湿度８５％の条件下での恒温恒湿槽（エスペック社ＬＨＬ－１１４）における２４０ｈ放置後（８５℃８５％ＲＨ密着）との、計２回実施した。
　評価基準は以下のとおりである。評価基準が「△」及び「×」以外は、硬化塗膜と試験基板の密着性が良好であり、評価基準が「◎」は特に密着性が良好なものである。
　　◎：ピール後のマス目は１００%付着したままであり、欠けは見られない
　　〇：ピール後のマス目は１００%付着したままであり、マス目の交差点にわずかな欠けが見られる
　　△：ピール後のマス目は１００%付着したままであり、マス目の交差点に剥がれが発生している
    ×：ピール後のマス目は１００％付着したままではない。
　結果を下記表２に示す。 [cross cut]
In accordance with JIS K 5600-5-6 1999, the cured coating film on each test substrate of the curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 obtained in [Preparation of test substrate] was , Cut using a cross-cut guide for 1 mm intervals to create 25 squares (5 x 5) with a width of 1 mm in both the vertical and horizontal directions, and cut the transparent adhesive tape (width 25 ± 1 mm) into the squares of the cured coating film. Rub the tape firmly with your fingers so that the cured film is visible, and within 5 minutes after adhesion, firmly pull it away at an angle of approximately 60 degrees in 0.5 to 1.0 seconds (tape peeling). ), the condition of the grid was investigated.
The cross-cuts were made after being left at 23°C and 50% RH for 3 hours (initial adhesion) and after being placed in a constant temperature and humidity chamber (Espec LHL-114) under the conditions of 85°C and 85% relative humidity. ) and after standing for 240 hours (85° C., 85% RH in close contact).
The evaluation criteria are as follows. The evaluation criteria other than "△" and "x" indicate that the adhesion between the cured coating film and the test substrate is good, and the evaluation criteria of "◎" indicates that the adhesion is particularly good.
◎: The grid remains 100% adhered after peeling, and no chipping is observed. ○: The grid remains 100% adhered after peeling, and slight chipping is observed at the intersection of the grids. △: The squares after peeling remain 100% attached, and peeling occurs at the intersections of the squares. ×: The squares after peeling do not remain 100% attached.
The results are shown in Table 2 below.
［鉛筆硬度］
　［試験基板の作製］で得られた実施例１～１０および比較例１～４の硬化性樹脂組成物の各試験基板上の硬化塗膜の表面における鉛筆硬度について、ＪＩＳ　Ｋ　５６００－５－４　１９９９に準拠して測定を行い、下記のとおり評価した。評価基準が「×」以外は硬化塗膜の硬度が高く、判断基準が「◎」は特に高い硬度を示すものである。
　　◎：Ｈ以上
　　〇：ＨＢ
　　×：Ｂ以下
　結果を下記表２に示す。 [Pencil hardness]
Regarding the pencil hardness on the surface of the cured coating film on each test substrate of the curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 obtained in [Preparation of test substrate], JIS K 5600-5-4. 1999, and the evaluation was made as follows. Evaluation criteria other than "x" indicate high hardness of the cured coating film, and evaluation criteria "◎" indicates particularly high hardness.
◎:H or higher 〇:HB
×: B or less The results are shown in Table 2 below.
［ＵＶ硬化後の指触乾燥性（タック試験）］
　［試験基板の作製］で得られた実施例１～１０および比較例１～４の硬化性樹脂組成物の各試験基板上の硬化塗膜の指触乾燥性を下記のとおり評価した。評価基準が「×」以外は硬化塗膜表面の硬化性が良好であり、評価基準が「◎」は硬化塗膜表面の硬化性が特に良好なものを示す。
　　◎：指で触っても全く痕がつかない
　　〇：指で触って少し痕が付くが、実用上問題がない
　　×：指で触ってべた付きがあり、指に顔料成分が残る
　　結果を下記表２に示す。 [Dryness to the touch after UV curing (tack test)]
The dryness to the touch of the cured coating film on each test substrate of the curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 obtained in [Preparation of test substrates] was evaluated as follows. Evaluation criteria other than "x" indicate that the cured coating surface has good curability, and evaluation criteria of "◎" indicates that the cured coating surface has particularly good curability.
◎: No marks left when touched with fingers ○: Slight marks left when touched with fingers, but no practical problems ×: Sticky when touched with fingers, pigment components remain on fingers The results are shown in the table below. Shown in 2.
［ＯＤ値］
　［試験基板の作製］において、硬化後の膜厚：１０μｍまたは２０μｍに変更した以外は同様の方法で作製した実施例１～１０および比較例１～４の硬化性樹脂組成物の各試験基板上の硬化塗膜のＯＤ値を下記のとおり測定した。
　ガラス基版の硬化塗膜側を測定器に向けて透過濃度計（サカタインクスエンジニアリング社 製、型番：Ｘ－Ｒｉｔｅ　３６１Ｔ、光源波長：４００～８００ｎｍ）に装着してＯＤ値を評価した。
　その結果、硬化後の膜厚：１０μｍの各実施例および各比較例のＯＤ値は４以上6以下であり、硬化後の膜厚：２０μｍの各実施例および各比較例のＯＤ値は６以上であり、
黒色遮光剤用途として十分なＯＤ値であった。
尚、硬化後の膜厚：１０μｍまたは２０μｍは、［試験基板の作製］と同様の方法で、５μｍ毎インクジェットプリンタを用いて描画し次いでＵＶ硬化させて、所定の膜厚まで積み上げて形成したものである。 [OD value]
[Preparation of test substrates] On each test substrate of the curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4, which were prepared in the same manner except that the film thickness after curing was changed to 10 μm or 20 μm. The OD value of the cured coating film was measured as follows.
The OD value was evaluated by attaching the glass substrate to a transmission densitometer (manufactured by Sakata Inx Engineering Co., Ltd., model number: X-Rite 361T, light source wavelength: 400 to 800 nm) with the cured coating side of the glass substrate facing the measuring device.
As a result, the OD value of each Example and each Comparative Example with a film thickness of 10 μm after curing was 4 or more and 6 or less, and the OD value of each Example and each Comparative Example with a film thickness of 20 μm after curing was 6 or more. and
The OD value was sufficient for use as a black light shielding agent.
The film thickness after curing: 10 μm or 20 μm was formed by drawing on an inkjet printer every 5 μm using the same method as in [Preparation of test substrate], then curing with UV, and stacking up to a predetermined film thickness. It is.
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
　上記ＯＤ値の評価結果、および表２に示される結果から明らかなように、本発明の硬化性樹脂組成物を用いた各実施例おいては、高い遮光性に加えて、表面硬化性が良好であり、
高温高湿条件での安定した密着性を発揮し、且つ硬化後の硬度も高い硬化膜を形成できた。また、（ａ）分子内にエステル結合を有する脂環式エポキシ化合物と、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物の質量比をより好ましい範囲である８：１００～２５：１００とし、かつ（Ｂ）オキセタン化合物と、前記（Ａ）エポキシ化合物との質量比をより好ましい範囲である１０：１００～２０：１００とした実施例１、実施例３、実施例５、実施例６は、各評価結果が評価基準の内、最も良い結果となった。特に、高温高湿条件でのクロスカット（８５℃８５％ＲＨ密着）と鉛筆硬度について、他の実施例より優れる結果となった。 As is clear from the above evaluation results of OD value and the results shown in Table 2, in each example using the curable resin composition of the present invention, in addition to high light shielding property, surface curability was good. and
It was possible to form a cured film that exhibited stable adhesion under high temperature and high humidity conditions and had high hardness after curing. In addition, the mass ratio of (a) an alicyclic epoxy compound having an ester bond in the molecule and (b) an alicyclic epoxy compound having no ester bond in the molecule is in a more preferable range of 8:100 to 25: 100, and the mass ratio of the (B) oxetane compound and the (A) epoxy compound was set to a more preferable range of 10:100 to 20:100.Example 1, Example 3, Example 5, Example 6 had the best results among the evaluation criteria. In particular, the results were better than other examples in terms of cross-cutting (85° C., 85% RH adhesion) and pencil hardness under high temperature and high humidity conditions.
これに対して、（ａ）分子内にエステル結合を有する脂環式エポキシ化合物と、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物の質量比が範囲外の４３：１００～５０：１００である比較例１乃至２および（ａ）分子内にエステル結合を有する脂環式エポキシ化合物を含まない比較例３は、実施例に対して、クロスカット（初期密着）がやや劣り、高温高湿条件でのクロスカット（８５℃８５％ＲＨ密着）については、硬化塗膜が剥がれ、評価基準の内、最も悪い結果となった。また、比較例１乃至３は、鉛筆硬度も評価基準の内、最も悪い結果となった。
比較例４は、クロスカットの評価結果は良いものの、鉛筆硬度及びタックが、評価基準の内、最も悪い結果となった。 On the other hand, the mass ratio of (a) an alicyclic epoxy compound having an ester bond in the molecule and (b) an alicyclic epoxy compound having no ester bond in the molecule is outside the range of 43:100 to 50. :100, and Comparative Example 3, which does not contain an alicyclic epoxy compound having an ester bond in the molecule (a), was slightly inferior in cross-cut (initial adhesion) and Regarding cross-cutting under high humidity conditions (adhesion at 85° C. and 85% RH), the cured coating film peeled off, resulting in the worst result among the evaluation criteria. In addition, Comparative Examples 1 to 3 had the worst results in terms of pencil hardness among the evaluation criteria.
Comparative Example 4 had good cross-cut evaluation results, but pencil hardness and tack had the worst results among the evaluation criteria.

Claims (7)

  1. 　（Ａ）エポキシ化合物と、（Ｂ）オキセタン化合物と、（Ｃ）光酸発生剤と、（Ｄ）黒色着色剤とを含む硬化性樹脂組成物であって、
    　前記（Ａ）エポキシ化合物は、
    （ａ）分子内にエステル結合を有する脂環式エポキシ化合物と、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物とを、５：１００～３０：１００の数値範囲の質量比で含む、
    前記硬化性樹脂組成物。     A curable resin composition comprising (A) an epoxy compound, (B) an oxetane compound, (C) a photoacid generator, and (D) a black colorant,
    The epoxy compound (A) is
    (a) an alicyclic epoxy compound having an ester bond in the molecule and (b) an alicyclic epoxy compound having no ester bond in the molecule at a mass ratio in the numerical range of 5:100 to 30:100. include,
    The curable resin composition.
  2. 　５０℃にて５～２０ｍＰａ・ｓの粘度を有する、請求項１に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, which has a viscosity of 5 to 20 mPa·s at 50°C.
  3. 　前記（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物は、２官能のエポキシ基を有する、請求項１に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the (b) alicyclic epoxy compound having no ester bond in the molecule has a difunctional epoxy group.
  4. 　前記（Ｄ）黒色着色剤が、カーボンブラックであり、かつ前記（Ａ）エポキシ化合物と（Ｂ）オキセタン化合物の合計１００質量部に対して５質量部以上含まれる、請求項１または２に記載の硬化性樹脂組成物。 3. The black colorant (D) is carbon black, and is contained in an amount of 5 parts by mass or more based on a total of 100 parts by mass of the epoxy compound (A) and the oxetane compound (B). Curable resin composition.
  5. 　前記（Ｂ）オキセタン化合物と、前記（Ａ）エポキシ化合物との質量比が、２：１００～４０：１００の数値範囲にある、請求項１～３のうちいずれか１項に記載の硬化性樹脂組成物。 The curable resin according to any one of claims 1 to 3, wherein the mass ratio of the (B) oxetane compound to the (A) epoxy compound is in a numerical range of 2:100 to 40:100. Composition.
  6. 前記（Ａ）エポキシ化合物は、（ａ）分子内にエステル結合を有する脂環式エポキシ化合物と、（ｂ）分子内にエステル結合を有しない脂環式エポキシ化合物とを、８：１００～２５：１００の数値範囲の質量比で含む請求項５に記載の硬化性樹脂組成物。 The epoxy compound (A) is a mixture of (a) an alicyclic epoxy compound having an ester bond in the molecule, and (b) an alicyclic epoxy compound having no ester bond in the molecule, in a ratio of 8:100 to 25: The curable resin composition according to claim 5, wherein the curable resin composition is contained in a mass ratio in a numerical range of 100.
  7. 　前記（Ｂ）オキセタン化合物と、前記（Ａ）エポキシ化合物との質量比が、１０：１００～２０：１００の数値範囲にある、請求項６に記載の硬化性樹脂組成物。 The curable resin composition according to claim 6, wherein the mass ratio of the (B) oxetane compound to the (A) epoxy compound is in a numerical range of 10:100 to 20:100.
PCT/JP2023/011812 2022-03-24 2023-03-24 Curable resin composition WO2023182495A1 (en)

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JPH1161034A (en) * 1997-08-15 1999-03-05 Kansai Paint Co Ltd Coating composition and application method thereof
JP2000144043A (en) * 1998-11-09 2000-05-26 Toyo Ink Mfg Co Ltd Ultraviolet curable coating material and its use
JP2005194453A (en) * 2004-01-09 2005-07-21 Konica Minolta Medical & Graphic Inc Active light-curable composition, active light-curable ink jet ink, and method for image formation and printer using the same
JP2005264098A (en) * 2004-03-22 2005-09-29 Konica Minolta Medical & Graphic Inc Active ray-curable composition, image forming method using the same and inkjet recording apparatus using the same
JP2008138113A (en) * 2006-12-04 2008-06-19 Konica Minolta Medical & Graphic Inc Curable composition, active energy ray-curable composition, ink, active energy ray-curable inkjet ink, and method of forming image
JP2014196475A (en) * 2013-03-04 2014-10-16 株式会社ダイセル Photosensitive resin composition and cured product of the same, and optical component
WO2021049331A1 (en) * 2019-09-12 2021-03-18 太陽インキ製造株式会社 Curable composition for inkjet
WO2022059395A1 (en) * 2020-09-17 2022-03-24 株式会社Adeka Composition, cured product, and method for producing cured product

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1161034A (en) * 1997-08-15 1999-03-05 Kansai Paint Co Ltd Coating composition and application method thereof
JP2000144043A (en) * 1998-11-09 2000-05-26 Toyo Ink Mfg Co Ltd Ultraviolet curable coating material and its use
JP2005194453A (en) * 2004-01-09 2005-07-21 Konica Minolta Medical & Graphic Inc Active light-curable composition, active light-curable ink jet ink, and method for image formation and printer using the same
JP2005264098A (en) * 2004-03-22 2005-09-29 Konica Minolta Medical & Graphic Inc Active ray-curable composition, image forming method using the same and inkjet recording apparatus using the same
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JP2014196475A (en) * 2013-03-04 2014-10-16 株式会社ダイセル Photosensitive resin composition and cured product of the same, and optical component
WO2021049331A1 (en) * 2019-09-12 2021-03-18 太陽インキ製造株式会社 Curable composition for inkjet
WO2022059395A1 (en) * 2020-09-17 2022-03-24 株式会社Adeka Composition, cured product, and method for producing cured product

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