CN114341282A - Curable composition for inkjet - Google Patents
Curable composition for inkjet Download PDFInfo
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- CN114341282A CN114341282A CN202080062209.4A CN202080062209A CN114341282A CN 114341282 A CN114341282 A CN 114341282A CN 202080062209 A CN202080062209 A CN 202080062209A CN 114341282 A CN114341282 A CN 114341282A
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- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
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- 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
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- 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
- C08G59/22—Di-epoxy compounds
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- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Epoxy Resins (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
[ problem ] to provide a curable composition suitable for an inkjet process, which can be cured at a practical exposure amount, has a high hardness of a cured film after curing, and has a matte effect in addition to a suppressed glossiness of a black matrix used in an LED product. [ solution ] A curable composition characterized by containing: (A) a polyfunctional alicyclic epoxy compound, (B) an oxetane compound, (C) a cyclic siloxane compound having 4 or more epoxy groups, and (D) a photo cation polymerization initiator, wherein the OD value of the cured coating film at a film thickness of 10 to 20 μm is 4 or more.
Description
Technical Field
The present invention relates to a curable composition, and particularly to a curable composition for inkjet printing and a cured product thereof.
Background
In recent years, LED displays using mini LEDs having a size slightly larger than a micro LED and a side of approximately several hundred μm have been put to practical use.
For LED displays, in order to make the colors displayed as LED articles more clearly visible, the following techniques are utilized: after mounting on a substrate, a so-called black matrix is usually formed by applying a black ink composition to the gaps (approximately 200 μm) between the LEDs.
As such a technique, for example, patent document 1 proposes the following technique: the resin composition for a light shielding layer contains a black pigment such as carbon black, a dispersant and a thermosetting binder, and forms a black matrix without patterning by photolithography.
On the other hand, since a large number of LEDs are mounted, it is desirable to apply the black ink composition by an inkjet printing method from the viewpoint of production efficiency.
Here, the inkjet printing method is a method of: droplets of the curable composition are discharged onto a substrate using an ink jet printer, and then irradiated with active energy rays such as UV to be instantly cured. Further, the inkjet printing method can directly draw a predetermined print pattern from digital data, can reduce the amount of ink used, and does not require a screen printing plate, and therefore, can perform efficient production compared to the conventional method. Further, since the inkjet printing method is non-contact printing, printing is easily performed on substrates having irregularities or flexible substrates, and it is expected to be applied to materials for printed wiring boards.
As such a curable composition for inkjet, in order to stably perform inkjet discharge at room temperature and form a cured film having sufficient heat resistance and insulation properties by only light irradiation without heating, for example, patent document 2 proposes the following technique: contains a specific monofunctional polymerizable monomer and a specific polyfunctional polymerizable monomer.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2013-164457
Patent document 2: japanese patent application laid-open No. 2010-143982
Disclosure of Invention
Problems to be solved by the invention
Here, the property of the black matrix that reflects light and emits gloss is not preferable because the color of the LED may be damaged. Therefore, it is considered that a matting material is contained in a composition for forming a black matrix to suppress the gloss of a cured product.
However, since the matting material is large in size for its use, when it is contained in a composition, there is a fear that smooth discharge of the composition from an ink jet nozzle is inhibited.
In addition, similarly, from the viewpoint of smooth discharge, it is desirable to suppress the viscosity of the composition used.
In this regard, the technique described in patent document 1 does not disclose any solution to solve these problems at the same time.
On the other hand, the amount of active energy rays for curing the curable composition for ink jet is suppressed to approximately 2000mJ/cm2The exposure amount of (2) is practical. Furthermore, it is needless to say that the hardness of the cured product and the ratio of the cured product to the substrate are desiredThe adhesion was as excellent as possible.
However, the technique described in patent document 2 does not assume a curable composition that can be cured with a practical exposure amount and further provides a cured product having a higher hardness.
In view of the above, an object of the present invention is to provide a curable composition suitable for an inkjet printing method, which can form a cured product (for example, a cured film) that can be cured with a practical exposure amount, has not only high hardness, but also suppressed glossiness as a black matrix for LED products.
Means for solving the problems
The inventors have conducted intensive studies and, as a result, have found that: the present inventors have completed the present invention by solving the above problems by using a composition containing a specific polyfunctional alicyclic epoxy compound, an oxetane compound and a cyclic siloxane compound having 4 or more epoxy groups.
That is, the present invention relates to a curable composition containing:
(A) a polyfunctional alicyclic epoxy compound,
(B) An oxetane compound,
(C) A cyclic siloxane compound having 4 or more epoxy groups,
(D) A photo-cationic polymerization initiator, a polymerization initiator,
and the cured coating film has an OD value of 4 or more at a film thickness of 10 to 20 μm.
Among them, the curable composition having a viscosity of 5 to 20 mPas at 50 ℃ is preferable.
In another preferred embodiment, the curable composition has a 60-degree specular gloss of 60 or less on the surface of a coating film after curing.
Another preferred embodiment is the above curable composition wherein the arithmetic average surface roughness (Ra) of the surface of the cured coating film is 0.3 to 3.0. mu.m.
A more preferred embodiment is the above curable composition further containing (E) a photo cation sensitizer.
A particularly preferred embodiment is the above curable composition containing carbon black as a colorant in a range of 3.0 to 25.0% by mass relative to the mass of the entire solid components of the curable composition.
Still another embodiment relates to a cured product obtained from the curable composition.
Another aspect of the present invention relates to a curable composition containing:
(A) a polyfunctional alicyclic epoxy compound,
(B) An oxetane compound,
(C) A cyclic siloxane compound having 4 or more epoxy groups,
(D) A photo cation polymerization initiator, and
(E) a photo cation sensitizer.
The curable composition preferably has a viscosity of 5 to 20 mPas at 50 ℃.
Furthermore, it is preferable that the curable composition has a wavelength of 395nm of 2000mJ/m2The exposure amount of (2) is cured.
In the curable composition, the photo cation sensitizer (E) is preferably an alkoxy anthracene sensitizer.
The present invention also relates to a cured product obtained from the curable composition.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a curable composition which is suppressed in viscosity to a low level and can be cured at a practical exposure amount; and a cured product of the curable composition having high hardness, high OD value, and suppressed gloss.
Therefore, the curable composition of the present invention is expected to be suitably used as a material for inkjet printing for forming a matte cured coating film for a black matrix of an LED product, for example.
Detailed Description
The curable composition of the present invention mainly contains: (A) and (C) a cyclic siloxane compound having 4 or more epoxy groups, wherein the curing rate and the curing shrinkage are different from each other.
(A) When the polyfunctional alicyclic epoxy compound (D) generates an acid by the photo cationic polymerization initiator upon irradiation with light, the ring-opening polymerization of the epoxy group is started and curing shrinkage proceeds more rapidly than in the case of the oxetane compound (B). In addition, similarly to the component (a), the cyclic siloxane compound (C) having 4 or more epoxy groups undergoes curing shrinkage faster than the oxetane compound (B).
On the other hand, since the oxetane compound (B) has a four-membered ring structure, the volume shrinkage at the time of curing after light irradiation is small as compared with the epoxy compound, and the time for starting curing is also slow, it is presumed that the difference is a factor that a shape such as so-called wrinkle or fold can be formed on the surface of the coating film after completion of curing.
The black level of the curable composition of the present invention is high, and the OD value at a film thickness of 10 to 20 μm after curing is 4 or more, and the light transmittance is low, so that the light hardly reaches the deep part of the coating film at the time of light irradiation, and the difference in curing speed of each component at the time of light irradiation is likely to occur, which is also presumed to be a factor that can form a shape such as so-called wrinkles or folds on the surface of the coating film after curing.
As described above, when the curable composition of the present invention is cured depending on the composition thereof, the surface of the coating film is not completely smooth but is formed into a shape such as wrinkles or folds, and it is considered that this can diffuse various light from the outside, and exhibits the same effect as that of matting, and can form a matte cured coating film having a good gloss suppressed to a low level.
The curable composition of the present invention is characterized in that the OD value of the cured coating film is 4 or more, preferably 5 or more, at a film thickness of 10 to 20 μm, from the viewpoint of suppressing light reflection as a material for a black matrix used in LED products.
The OD value can be calculated by measuring the amount of transmitted light using a transmission type densitometer (model: X-Rite 361T; light source wavelength 400 to 800 nm; manufactured by Sakata Inx Engineering Corporation) and calculating the OD value on the basis of the formula-log 10 (T/100).
In addition, from the viewpoint of roughening of a cured product (cured coating film), the surface of the cured product (cured coating film) preferably shows a value of 60 or less, more preferably 35 or less, in terms of a film thickness of 10 μm after curing, by a 60-degree specular gloss meter according to ASTM D523-89 or ISO 2813.
In the curable composition of the present invention, the arithmetic average surface roughness (Ra) of the surface of the cured product (cured coating) is preferably 0.3 to 3.0 μm from the viewpoint of the balance between the surface roughening and OD value of the cured product (cured coating). When the arithmetic average surface roughness (Ra) of the surface of the cured product (cured coating film) is within the above range, the OD value of the cured coating film at a film thickness of 10 to 20 μm and the 60-degree specular gloss of the surface of the cured product (cured coating film) according to ASTM D523-89 or ISO 2813 are each a numerical value within the above range.
Further, the curable composition of the present invention is premised on its applicability to an inkjet process in principle. Therefore, from the viewpoint of smooth discharge from the ink jet nozzle, the viscosity thereof is preferably in the range of 5 to 20 mPas at 50 ℃, more preferably in the range of 5 to 15 mPas at 50 ℃.
The viscosity can be measured, for example, using a cone-plate viscometer (TVE-33H manufactured by Toyobo industries Co., Ltd.).
Further, the curable composition of the present invention comprises (A) a polyfunctional alicyclic epoxy compound, (B) an oxetane compound, (C) a cyclic siloxane compound having 4 or more epoxy groups, (D) a photocationic polymerization initiator and (E) a photocationic sensitizer, and the resulting cured product has not only higher hardness and adhesion but also approximately 2000mJ/m at a wavelength of approximately 395nm2The exposure amount of (2) is cured.
The respective components of the curable composition of the present invention having the above-described characteristics will be described below.
[ (A) polyfunctional alicyclic epoxy Compound ]
In the present invention, by adding (a) a polyfunctional alicyclic epoxy compound to a curable composition, the hardness of a cured product obtained from the curable composition can be improved.
In the present invention, (a) the polyfunctional alicyclic epoxy compound is a compound having a total of 2 or more ethylene oxide groups represented by the following structural formula and/or cyclohexene oxide groups represented by the following structural formula in a molecule:
examples of the compound having an oxirane group represented by the above structural formula include compounds having the following structures:
examples of the epoxycyclohexylalkyl group-containing compound having the structural formula include compounds having any of the following structures:
(wherein A represents an alkylene group having 1 to 8 carbon atoms; and n1 and n2 each represent an integer of 1 to 30).
As the (A) polyfunctional alicyclic epoxy compound, commercially available products can be used, of course.
Examples thereof include terpene diene oxide (LDO) (manufactured by SYMRISE Corporation), CELLOXIDE2021P, CELLOXIDE 2081 and Epolide GT401 (both manufactured by Daicel Co., Ltd.), Syna Epoxy 06E, Syna Epoxy 21 and Syna Epoxy 28 (both manufactured by SYNASIA Corporation), and THI-DE (JX Nippon Oil & Energy Corporation).
In addition, from the viewpoint of further improving the hardness of the cured film, it is also preferable to use any 1 compound of the formulae a2 to a10 in combination with the compound represented by the formula a 1.
In this case, the mass ratio of the compound represented by the formula a1 to any 1 compound of the formulae a2 to a10 is 100: 0 to 50: 50. preferably 100: 0-80: 20.
the total content of the polyfunctional alicyclic epoxy compound (a) is 10 to 90% by mass, preferably 30 to 60% by mass, based on the total solid content of the curable composition, from the viewpoint of hardness of the cured product.
[ (B) Oxetane Compound ]
In the curable composition of the present invention, it is considered that the use of the polyfunctional alicyclic epoxy compound (a) and the oxetane compound (B) in combination makes it possible to form a shape such as wrinkles or folds in a cured product (cured coating film).
As the oxetane compound (B), both monofunctional ones and polyfunctional ones can be used.
Examples of the monofunctional oxetane compound include 3-methyloxetane, 3-ethyloxetane, 3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane and 3-ethyl-3-hydroxymethyloxetane.
In addition, as the polyfunctional oxetane compound, 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-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, methyl (3-ethyl-3-oxetanyl) methacrylate, methyl (3-ethyl-3-oxetanyl) acrylate, methyl (3-oxetanyl) methacrylate, and the like are exemplified, In addition to polyfunctional oxetanes such as oligomers and copolymers thereof, there may be mentioned etherates of oxetanol and hydroxyl group-containing resins such as novolak resins, poly (p-hydroxystyrene), Cardo-type bisphenols, calixarenes, and silsesquioxanes. Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate, and the like can be mentioned.
As the oxetane compound (B), for example, OXT-101 and OXT-221 (both manufactured by Toyo Synthesis Co., Ltd.) or the following formula can be used:
commercially available products such as TR-TCM-207 (manufactured by TRONLY Co., Ltd.).
Among them, from the viewpoint of more favorably suppressing the gloss of the cured product, a polyfunctional one is preferable to a monofunctional one.
However, it is of course also possible to use both monofunctional and polyfunctional.
The content of the oxetane compound (B) is 5 to 70% by mass, preferably 10 to 50% by mass based on the total solid content of the curable composition from the viewpoint of hardness and gloss of a cured product.
[ (C) Cyclic siloxane Compound having 4 or more epoxy groups ]
The curable composition of the present invention contains (C) a cyclic siloxane compound having 4 or more epoxy groups, and thus can improve the adhesion between a cured product (cured coating film) and a substrate.
Such (C) cyclic siloxane compound having 4 or more epoxy groups has a siloxane-based bond:
-Si-O-Si-
the cyclic structure of (3) may also include a tetramer, a pentamer, or a multimer thereof. Further, 4 or more epoxy groups are bonded to a chain extending from each Si atom of such a cyclic siloxane structure.
Examples of these include those having structures represented by the following formulae (1), (2) and (3) (corresponding to tetramer, pentamer and hexamer, respectively).
(in the formula, R1、R3、R5And R7Is an epoxy-containing group, R2、R4、R6And R8Each independently is a hydrocarbon group, preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group. )
(in the formula, R1、R3、R5、R7And R94 or 5 of (a) are all epoxy-containing groups, there being R of non-epoxy-containing groups1、R3、R5、R7Or R9In the case of (A), it is a hydrocarbon group, preferably an alkyl group having 1 to 3 carbon atoms, R2、R4、R6、R8And R10Each independently is a hydrocarbon group, preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group. )
(in the formula, R1、R3、R5、R7、R9And R114, 5 or 6 of which are all epoxy-containing groups, there being R of non-epoxy-containing groups1、R3、R5、R7、R9Or R11In the case of (A), it is a hydrocarbon group, preferably an alkyl group having 1 to 3 carbon atoms, R2、R4、R6、R8、R10And R12Each independently is a hydrocarbon group, preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group. )
Examples of the epoxy-containing group include glycidoxymethyl group, glycidoxyethyl group, and glycidoxypropyl group.
Specific examples thereof include those having the following structures.
As the epoxy-containing group, an alicyclic epoxy group is more preferable. Examples of the (C) cyclic siloxane compound having 4 or more epoxy groups, which has such an alicyclic epoxy group, include those having the following structures:
as the (C) cyclic siloxane compound having 4 or more epoxy groups, a commercially available product such as KR-470 (manufactured by shin-Etsu chemical Co., Ltd.) can be used.
In addition, 2 or more of (C) cyclic siloxane compounds having 4 or more epoxy groups may be used in combination.
The content of the cyclic siloxane compound having 4 or more epoxy groups (C) is 1 to 30% by mass, preferably 3.0 to 15% by mass, based on the total solid content of the curable composition, from the viewpoint of hardness and gloss of the cured product.
[ (D) photo cation polymerization initiator ]
Examples of the photo-cationic polymerization initiator include onium salts such as diazonium salts, iodonium salts, bromonium salts, chloronium salts, sulfonium salts, selenium salts, pyrylium salts, thiopyrylium (thiapyrylium) salts, and pyridinium salts; halogenated compounds such as tris (trihalomethyl) -s-triazine and derivatives thereof; 2-nitrobenzyl ester of sulfonic acid; an imidosulfonate; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivatives; n-hydroxyimide ═ sulfonate; tris (methylsulfonyloxy) benzene derivatives; bis-sulfonyl diazomethanes; sulfonyl carbonyl alkanes; sulfonylcarbonyldiazomethanes; disulfone compounds, and the like.
These photopolymerization initiators may be used alone or in combination of 2 or more.
Examples of commercially available photocationic polymerization initiators (D) include CPI-100P, CPI-200K, CPI-101A (see above, manufactured by San-Apro Ltd.), Cyracure photoinitiator UVI-6990, Cyracure photoinitiator UVI-6992, Cyracure photoinitiator UVI-6976 (see above, manufactured by Dow Chemical Japan Co., Ltd.), Adeka Opomer SP-150, Adeka Opomer SP-152, Adeka Opomer SP-170, Adeka Opomer SP-172 (see above, manufactured by Asahi electro-Chemical Co., Ltd.), CI-5102, CI-2855 (see above, manufactured by Nippon Kao Co., Ltd.), Sunaid SI-60L, Sunaid SI-80L, Sunaid SI-100L, Sunaid-110L, Sunaid SI-180L, Sunaid SI-145 and Sunaid SI-180, sanxin chemical industry Co., Ltd.), Esacure 1064, Esacure 1187 (Lamberti Co., Ltd.), OMNICA 432, OMNICA 440, OMNICA 445, OMNICA 550, OMNICA 650, OMNICA BL-550(IGM RESINS LIMITED), IRGACURE 250 (manufactured by BASF corporation), Rhodorsil PHOTOITIATOR 2074 (manufactured by Rhodorsil Japan K.K.), WPI-113, WPI-116, WPI-169, and WPI-170 (manufactured by Wako pure chemical industries, Ltd.), and the like.
Among them, CPI-100P, CPI-101A, CPI-200K, CPI-210S manufactured by San-Apro Ltd, IRGACURE 250 manufactured by BASF corporation as an aromatic iodonium salt, and WPI-113, WPI-116, WPI-169 and WPI-170 manufactured by Wako pure chemical industries are preferable.
(D) The content of the photo cation polymerization initiator is 3.5 to 13% by mass, preferably 3.8 to 6% by mass based on the total solid content of the curable composition.
The content of the photo cation polymerization initiator (D) is preferably 4.1 to 12% by mass, more preferably 4.3 to 7.5% by mass, based on the total solid content of the polyfunctional alicyclic epoxy compound (a), the oxetane compound (B) and the cyclic siloxane compound having 4 or more epoxy groups (C) in the curable composition.
[ (E) Photocationic sensitizer ]
In order to further improve the photosensitivity, the curable composition of the present invention may further contain (E) a photocationic sensitizer.
The (E) photo cation sensitizer is preferably a compound which is in an excited state by light having a wavelength of 350 to 450 nm. Examples thereof include polycyclic aromatic compounds such as pyrene, perylene, benzo [9,10] phenanthrene and anthracene; xanthenes such as fluorescein, eosin, erythromycin, rhodamine B, rose bengal and the like; xanthenes such as xanthone, thioxanthone, dimethylthioxanthone, and diethylthioxanthone; cyanines such as thiacarbocyanine and oxacarbocyanine; merocyanines such as merocyanine and carbon merocyanine; (ii) rhodanocyanines; (ii) oxoquinolines; thiazines such as thionine, methylene blue, and toluidine blue; acridines such as acridine orange, flavin, and acriflavine; acridones such as acridone and 10-butyl-2-chloroacridone; anthraquinones; squarylium species; styrenes; a base styrenic; coumarins such as 7-diethylamino-4-methylcoumarin. Among them, preferred are anthracene compounds, of which alkoxyanthracene is more preferred, and particularly preferred is one having the following structure:
these (E) photo cation sensitizers may be used in combination of 2 or more thereof.
As the (E) photo cation sensitizer, commercially available ones can also be used. Examples of such a compound include Anthracure (registered trademark) UVS-1101 (diethoxyanthracene; manufactured by Kawasaki chemical Co., Ltd.), Anthracure (registered trademark) UVS-1221 (dipropoxyanthracene; manufactured by Kawasaki chemical Co., Ltd.), and Anthracure (registered trademark) UVS-1331 (dibutoxyanthracene; manufactured by Kawasaki chemical Co., Ltd.).
(E) The content of the photo cation sensitizer is 0.1 to 2.0 parts by mass, preferably 0.2 to 1.0 part by mass, based on 1 part by mass of the photo cation polymerization initiator (D).
The content of the (E) photo cation sensitizer is preferably more than 0 and 6 mass% or less, more preferably more than 1.0 mass% and 3.0 mass% or less, based on the total solid content of the (a) polyfunctional alicyclic epoxy compound, (B) oxetane compound, and (C) cyclic siloxane compound having 4 or more epoxy groups in the curable composition.
[ coloring agent ]
The curable composition of the present invention usually contains a colorant from the viewpoint of the characteristics as a black matrix. Typically, a black-based colorant such as carbon black is used, but the OD value of the cured product may be 4 or more at a film thickness of 10 μm to 20 μm, and particularly may be 4 or more at a thinner film thickness of 10 μm, and other colorants may be contained instead of the black-based colorant, or may be added to the carbon black and further contained.
Examples of the black coloring agent include, in addition to carbon black, iron oxide (Fe)3O4) Inorganic pigments such as black titanium oxide, copper manganese black, copper chromium black, and cobalt black, and organic pigments such as cyanine black and aniline black.
Examples of the other coloring agents include red, blue, green, and yellow pigments and dyes which are generally known.
The content of the colorant in the curable composition of the present invention may be adjusted in consideration of the OD value of the cured product and/or the gloss of the cured product, and is approximately 3.0 to 25.0 mass%, preferably 4.0 to 15.0 mass%, based on the total solid content of the curable composition.
[ other ingredients ]
The curable composition of the present invention may further contain, within a range not impairing the properties thereof: solvents, dispersants, thickeners, surfactants, antioxidants, plasticizers, flame retardants, antistatic agents, leveling agents, defoamers, and antimicrobial agents.
[ cured product and Process for producing the same ]
The curable composition of the present invention is applied to a target portion of a substrate according to an inkjet process, and then cured to form a cured product.
Curing can be performed by irradiating the applicable composition with active energy rays.
As the irradiation light source of the active energy ray, an LED, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is suitable. In addition, electron beams, α rays, β rays, γ rays, X rays, neutron beams, and the like can also be used. When the number of the irradiation light sources is 1 or2 or more, and 2 or more, it is needless to say that light sources having different wavelengths may be used in combination.
In addition, the exposure amount based on the active energy ray is usually 10 to 10000mJ/cm2Preferably 20 to 2000mJ/cm2More preferably 100 to 2000mJ/cm2Within the range of (1).
The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples.
Unless otherwise specified, "part" and "%" are based on mass.
Examples
The curable compositions of examples 1 to 9 and comparative examples 1 to 3 were prepared by mixing the respective materials in the amounts shown in table 1 below, and premixing the respective materials in a mixer. The numerical values of the blending amounts in the tables represent parts by mass of the solid components unless otherwise specified.
[ Table 1]
TABLE 1 composition of curable composition
In addition, the method is as follows: CELLOXIDE2021P (Daicel Co., Ltd.)
In addition, 2: LDO (manufactured by SYMRISE corporation)
And (2) in color: OXT-101 (manufactured by Toyo Synthesis Co., Ltd.)
In addition, 4: OXT-221 (manufactured by Toyo Synthesis Co., Ltd.)
In addition, the method is as follows: KBM-403 (manufactured by Xinyue chemical Co., Ltd.)
In addition, 6: BYK-315N (BYK Japan K.K.)
In addition, the color is 7: carbon Black Pigment Black7
In addition, the color is 8: KR-470 (manufactured by Xinyue chemical Co., Ltd.)
In addition, the color is 9: CPI-100P (solid content 50%) (manufactured by San-Apro Ltd.)
In addition, the color is 10: UVS-1101 (Kawasaki chemical industry Co., Ltd.)
From the thus obtained curable compositions of examples 1 to 9 and comparative examples 1 to 3, cured products (cured coating films) having film thicknesses of 10 μm and 20 μm were obtained, and the gloss, OD value, and pencil hardness were measured for the cured products as described below. The viscosity at 50 ℃ of each curable composition before curing was also measured.
[ production of test substrate ]
The curable compositions of examples 1 to 9 and comparative examples 1 to 3 were drawn on a substrate using an ink jet printer under the following conditions, and then UV-cured to prepare test substrates, respectively. A glass substrate is used as a base material.
Drawing conditions based on ink jet printer
Film thickness after curing: 10 μm or20 μm
The device comprises the following steps: using a piezoelectric ink jet Printer (Materials Printer DMP-2831 (head temperature 50 ℃ C.) manufactured by Fuji film Co., Ltd.)
UV curing conditions
LED-UV lamp (FireEdge FE400 manufactured by Phoseon TECHNOLOGY Co.)
Illuminance: 6000mW/cm2
Exposure amount: 1000mJ/cm2
Wavelength: 395nm
[ gloss ]
The surface of each test substrate was measured for 60-degree gloss (gloss value) using Micro-tri-gross (BYK Japan K.K.). The 60-degree gloss is expressed by rounding the 1 st position after the decimal point of the average value to an integer.
Good quality of 60 or less in gloss
Gloss of over 60
The results are shown in tables 2 and 3 below.
[ OD value ]
The coated side of the glass substrate was attached to a transmission type densitometer (model: X-Rite 361T manufactured by Sakata Inx Engineering Corporation, light source wavelength: 400 to 800nm) with a film side facing the measuring instrument, and the OD value was evaluated.
Has OD value of 6 or more
Good quality of 4 or more and less than 6 in OD
OD value less than 4
The results are shown in tables 2 and 3 below.
[ Pencil hardness ]
The pencil hardness of the surface of the obtained cured coating film was measured in accordance with JIS K5600-5-4.
The results are shown in tables 2 and 3 below.
[ viscosity at 50 ℃ C ]
The viscosity of the curable compositions of examples 1 to 9 and comparative examples 1 to 3 was measured at an ink temperature of 50 ℃ and a speed of 100rpm using a cone-plate viscometer (TVE-33H manufactured by Toyobo industries Co., Ltd.).
[ arithmetic average surface roughness (Ra) [ mu ] m ]
The surface shape of the cured coating film thus obtained was measured with a shape measuring laser microscope (VK-X100) and an observation application program (VK-H1VX) manufactured by KEYENCE CORPORATION under an objective lens having a magnification of 50 times, and the arithmetic mean surface roughness (Ra) was determined from the data thus obtained by an analysis application program (VK-H1XA) manufactured by the same company according to the formula JIS B0601-2001. In this case, the measurement region is defined as the entire region, and both λ s and λ c are defined as none with respect to the cutoff value.
The results are shown in tables 2 and 3 below.
[ Table 2]
TABLE 2 test JI fruit 1 (film thickness 10 μm)
[ Table 3]
TABLE 3 fruit 2 test (film thickness 20 μm)
The curable compositions of examples 10 to 25 and comparative examples 4 to 6 were prepared by separately mixing the respective materials in accordance with the mixing amounts shown in table 4 below and premixing the respective materials in a mixer. The numerical values of the blending amounts in the tables represent parts by mass of the solid components unless otherwise specified.
[ Table 4]
TABLE 4 composition of the curable compositions (II)
In addition, the method is as follows: CELLOXIDE2021P (Daicel Co., Ltd.)
In addition, 2: LDO (manufactured by SYMRISE corporation)
And (2) in color: THI-DE (manufactured by JX Nippon Oil & Energy Corporation)
In addition, 4: OXT-101 (manufactured by Toyo Synthesis Co., Ltd.)
In addition, the method is as follows: OXT-221 (manufactured by Toyo Synthesis Co., Ltd.)
In addition, 6: TR-TCM-207(TRONLY, manufactured by TRONLY Co., Ltd.)
In addition, the color is 7: KBM-403 (manufactured by Xinyue chemical Co., Ltd.)
In addition, the color is 8: BYK-315N (BYK Japan K.K.)
In addition, the color is 9: carbon Black Pigment Black7
In addition, the color is 10: KR-470 (manufactured by Xinyue chemical Co., Ltd.)
The method is characterized in that: x-40-2678 (manufactured by shin-Yue chemical Co., Ltd.)
The method is characterized by being in color in 12: CPI-100P (solid content 50%) (manufactured by San-Apro Ltd.)
The color is as follows: UVS-1331 (Kawasaki chemical industry Co., Ltd.)
The color is 14: UVS-1101 (Kawasaki chemical industry Co., Ltd.)
Cured products (cured coating films) were obtained from the thus obtained curable compositions of examples 10 to 25 and comparative examples 4 to 6, and the cured products were measured for finger-touch dryness, pencil hardness, and cross cut as described below. The viscosity at 50 ℃ of each curable composition before curing was also measured.
[ production of test substrate ]
The curable compositions of examples 10 to 25 and comparative examples 4 to 6 were drawn on a substrate using an ink jet printer under the following conditions, and then UV-cured to prepare test substrates, respectively. A glass substrate is used as a base material.
Drawing conditions based on ink jet printer
Film thickness: 10 μm
The device comprises the following steps: using a piezoelectric ink jet Printer (Materials Printer DMP-2831 (head temperature 50 ℃ C.) manufactured by Fuji film Co., Ltd.)
UV curing conditions
LED-UV lamp (FireEdge FE400 manufactured by Phoseon TECHNOLOGY Co.)
Exposure amount: 5000mJ/cm2、1000mJ/cm2、2000mJ/cm2、5000mJ/cm2、10000mJ/cm2
Wavelength: 395nm
[ finger-touch drying Property after UV curing ]
The cured coating film obtained was evaluated for finger-touch dryness.
O: no trace even if touched with a finger
X: sticky to touch with fingers
Blank column: not cured
The results are shown in table 5 below.
[ viscosity at 50 ℃ C ]
The viscosity of the curable compositions of examples 10 to 25 and comparative examples 4 to 6 at an ink temperature of 50 ℃ and at 100rpm was measured using a cone-plate viscometer (TVE-33H, manufactured by Toyobo industries Co., Ltd.).
[ Pencil hardness ]
The pencil hardness of the surface of the obtained cured coating film was measured in accordance with JIS K5600-5-4. The above H is recorded as qualified.
The results are shown in table 5 below.
[ ruling lattice ]
The obtained cured coating film was cut in accordance with JIS K5600-5-6 to prepare 25 (5X 5) cells each having a width of 1mm in the vertical and horizontal directions, and the state of the cells was examined. The evaluation criteria are as follows.
Classification 0: the cut edges were completely smooth and the mesh of any lattice was not peeled.
Classification 1: small peeling of the coating film in the cutting intersection point was generated. The affected part of the cross section is definitely not higher than 5%.
And (4) classification 2: the coating film peels along the cut edges, and/or at the intersection points. The affected part in the cross-hatched part clearly exceeds 5% but is not higher than 15%.
And (3) classification: the coating film is peeled off along the cut edge, partially or entirely, and/or partially or entirely, each part of the mesh. The affected part in the cross-hatched part clearly exceeds 15% but is not higher than 35%.
And 4, classification: the coating film is peeled off along the cut edge, partially or entirely, and/or partially or entirely through the mesh at a plurality of positions. The affected part in the cross-hatched part clearly exceeded 35% but not more than 65%.
And (5) classification: large peeling of class 4 or more occurred.
[ Table 5]
TABLE 5 fruit 3 of test
Claims (13)
1. A curable composition characterized by containing:
(A) a polyfunctional alicyclic epoxy compound,
(B) An oxetane compound,
(C) A cyclic siloxane compound having 4 or more epoxy groups,
(D) A photo-cationic polymerization initiator, a polymerization initiator,
and the cured coating film has an OD value of 4 or more at a film thickness of 10 to 20 μm.
2. The curable composition according to claim 1, which has a viscosity of 5 to 20 mPas at 50 ℃.
3. The curable composition according to claim 1 or2, wherein the 60-degree specular gloss of the surface of the cured coating film is 60 or less.
4. The curable composition according to any one of claims 1 to 3, wherein the arithmetic average surface roughness (Ra) of the surface of the cured coating film is 0.3 to 3.0 μm.
5. The curable composition according to any one of claims 1 to 4, further comprising (E) a photo cation sensitizer.
6. The curable composition according to any one of claims 1 to 5, which contains carbon black as a colorant.
7. The curable composition according to claim 6, wherein the content of the carbon black is 3.0 to 25.0% by mass based on the mass of the entire solid content of the curable composition.
8. A cured product obtained from the curable composition according to claim 1 to 7.
9. A curable composition characterized by containing:
(A) a polyfunctional alicyclic epoxy compound,
(B) An oxetane compound,
(C) A cyclic siloxane compound having 4 or more epoxy groups,
(D) A photo cation polymerization initiator, and
(E) a photo cation sensitizer.
10. The curable composition according to claim 9, which has a viscosity of 5 to 20 mPas at 50 ℃.
11. The curable composition according to claim 9 or 10, which is capable of exhibiting 2000mJ/m at a wavelength of 395nm2The exposure amount of (2) is cured.
12. The curable composition according to any one of claims 9 to 11, wherein the (E) photo cation sensitizer is an alkoxy anthracene sensitizer.
13. A cured product obtained from the curable composition according to any one of claims 9 to 12.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-166458 | 2019-09-12 | ||
| JP2019166451 | 2019-09-12 | ||
| JP2019-166451 | 2019-09-12 | ||
| JP2019166458 | 2019-09-12 | ||
| JP2020094182A JP7455669B2 (en) | 2019-09-12 | 2020-05-29 | Curable composition for inkjet |
| JP2020-094182 | 2020-05-29 | ||
| JP2020094207A JP7446919B2 (en) | 2019-09-12 | 2020-05-29 | Curable composition for inkjet |
| JP2020-094207 | 2020-05-29 | ||
| PCT/JP2020/032719 WO2021049331A1 (en) | 2019-09-12 | 2020-08-28 | Curable composition for inkjet |
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| CN114341282A true CN114341282A (en) | 2022-04-12 |
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|---|---|---|---|
| CN202080062209.4A Pending CN114341282A (en) | 2019-09-12 | 2020-08-28 | Curable composition for inkjet |
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| Country | Link |
|---|---|
| KR (1) | KR20220063154A (en) |
| CN (1) | CN114341282A (en) |
| WO (1) | WO2021049331A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114958085A (en) * | 2021-02-18 | 2022-08-30 | 东友精细化工有限公司 | Photocurable ink composition, sealing layer, and image display device |
| CN115466543A (en) * | 2022-10-19 | 2022-12-13 | 浙江福斯特新材料研究院有限公司 | Packaging composition for photocuring black ink-jet, packaging structure and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TW202346404A (en) * | 2022-03-24 | 2023-12-01 | 日商太陽控股股份有限公司 | Curable resin composition |
| WO2023188856A1 (en) * | 2022-03-30 | 2023-10-05 | ナトコ株式会社 | Ink composition, light-blocking member and image display device |
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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 |
| CN104540868A (en) * | 2012-08-31 | 2015-04-22 | 株式会社大赛璐 | Curable composition, cured product thereof, optical member and optical device |
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| JP2010143982A (en) | 2008-12-17 | 2010-07-01 | Chisso Corp | Photo-curable ink for inkjet |
| JP2013164457A (en) | 2012-02-09 | 2013-08-22 | Dainippon Printing Co Ltd | Resin composition for light-shielding layer formation, color filter comprising light-shielding layer composed of resin composition for light-shielding layer formation, and display device comprising color filter |
| US10976663B2 (en) * | 2016-09-29 | 2021-04-13 | Kaneka Corporation | Photosensitive composition, colored pattern and method for producing same |
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2020
- 2020-08-28 WO PCT/JP2020/032719 patent/WO2021049331A1/en active Application Filing
- 2020-08-28 CN CN202080062209.4A patent/CN114341282A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104540868A (en) * | 2012-08-31 | 2015-04-22 | 株式会社大赛璐 | Curable composition, cured product thereof, optical member and optical device |
| 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 |
Non-Patent Citations (1)
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| 李子东等: "《实用胶粘剂原料手册》", vol. 1, 国防工业出版社, pages: 59 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114958085A (en) * | 2021-02-18 | 2022-08-30 | 东友精细化工有限公司 | Photocurable ink composition, sealing layer, and image display device |
| CN114958085B (en) * | 2021-02-18 | 2024-03-29 | 东友精细化工有限公司 | Photocurable ink composition, encapsulation layer, and image display device |
| CN115466543A (en) * | 2022-10-19 | 2022-12-13 | 浙江福斯特新材料研究院有限公司 | Packaging composition for photocuring black ink-jet, packaging structure and application thereof |
| CN115466543B (en) * | 2022-10-19 | 2024-02-27 | 福斯特(安吉)新材料有限公司 | Photocurable black inkjet packaging composition, packaging structure and application thereof |
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| KR20220063154A (en) | 2022-05-17 |
| WO2021049331A1 (en) | 2021-03-18 |
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